TW202332751A - Adhesive composition, laminate, method for manufacturing laminate, and method for manufacturing electronic component having high heat resistance and facilitating the removal of an adhesive layer - Google Patents

Abstract

This invention aims to provide an adhesive composition in which a separation layer is not needed, a laminate made by using the adhesive composition, a method for manufacturing the laminate, and a method for manufacturing an electronic component using the adhesive composition. The solution of this invention is an adhesive composition used for forming an adhesive layer that temporarily bonds a semiconductor substrate or an electronic device to a support through which a light can be transmitted, wherein the adhesive composition contains an urethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator (A), and the urethane resin (P1) has a structural unit (u1) containing a structure capable of absorbing at least partial light having a wavelength of 300-800 nm.

Description

Adhesive composition, laminated body, manufacturing method of laminated body, and manufacturing method of electronic components

The present invention relates to an adhesive composition, a laminated body, a manufacturing method of the laminated body, and a manufacturing method of electronic components.

Semiconductor packages (electronic components) including semiconductor elements exist in various forms according to corresponding sizes, such as WLP (Wafer Level Package), PLP (Panel Level Package), etc. Examples of semiconductor packaging technologies include fan-in technology and fan-out technology. As a semiconductor package based on fan-in technology, known are fan-in WLP (Fan-in Wafer Level Package), which rearranges terminals at the end of a bare chip in the chip area. As a semiconductor package based on fan-out technology, a fan-out WLP (Fan-out Wafer Level Package) in which the terminals are rearranged outside the chip area is known.

In recent years, fan-out technology in particular has attracted attention as a method that can achieve further high integration, thinning, and miniaturization of semiconductor packaging. For example, it is applied to arranging semiconductor elements on a panel and packaging them. Fan-out PLP (Fan-out Panel Level Package, Fan-out Panel Level Package), etc.

In order to achieve miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in the assembled components. However, if the thickness of the substrate is reduced, its strength will be reduced, and damage to the substrate may easily occur when manufacturing semiconductor packages. In this regard, a technique is known that temporarily adheres a substrate to a support using an adhesive, processes the substrate, and then separates the substrate from the support.

As an adhesive used for temporarily bonding a substrate and a support, a thermoplastic adhesive is often used because the adhesive layer can be easily removed using 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 technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2016/052315

[Problem to be solved by the invention]

If it is a previous adhesive, a separation layer is usually required to separate the support from the substrate after the substrate is processed. Therefore, it is necessary to form the separation layer and the adhesive layer separately, which is a complicated operation.

The present invention was made in view of the above situation, and its object is to provide an adhesive composition that does not require a separation layer, a laminated body manufactured using the adhesive composition, a method for manufacturing the laminated body, and an adhesive composition using the adhesive composition. Methods of manufacturing electronic components of objects. [Technical means to solve problems]

In order to solve the above-mentioned problems, the present invention adopts the following structure. That is, the first aspect of the present invention is an adhesive composition for forming an adhesive layer that temporarily connects a semiconductor substrate or an electronic device and a support capable of transmitting light, and the adhesive composition contains polymerizable carbon. - Polyurethane resin (P1) with carbon unsaturated bonds, and polymerization initiator (A). The polyurethane resin (P1) has a structural unit (u1) containing a structure capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm. ).

A second aspect of the present invention is a laminated body in which a support capable of transmitting light, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, and the adhesive layer is a cured product of the adhesive composition of the first aspect. .

A third aspect of the present invention is a method for manufacturing a laminated body, which is a method for manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are sequentially laminated. The manufacturing method includes the following steps: The step of applying the adhesive composition of the first aspect to a support or a semiconductor substrate to form an adhesive composition layer; the step of placing the semiconductor substrate on the support via the adhesive composition layer; and, The step of hardening the adhesive composition layer to form the adhesive layer.

A fourth aspect of the present invention is a method for manufacturing a laminated body in which a support capable of transmitting light, an adhesive layer, and an electronic device are sequentially laminated. After obtaining the laminated body, the manufacturing method further includes an electronic device forming step of forming an electronic device, which is a composite body including a metal or semiconductor component and a resin that seals or insulates the component.

A fifth aspect of the present invention is a manufacturing method of an electronic component, which, after obtaining the laminated body by the manufacturing method of the laminated body of the fourth aspect, includes the following steps: irradiating the above-mentioned adhesive layer with light through the above-mentioned support body; The step of modifying the above-mentioned adhesive layer to separate the above-mentioned electronic device from the above-mentioned support; and using an acid or alkali to decompose the urethane bond in the above-mentioned adhesive layer, thereby decomposing the urethane bond attached to the above-mentioned electronic device. The above steps for removing the adhesive layer. [Effects of the invention]

According to the present invention, it is possible to provide an adhesive composition that can easily remove an adhesive layer without requiring a separation layer, a laminated body manufactured using the adhesive composition, a method for manufacturing the laminated body, and an adhesive composition using the adhesive composition. Manufacturing method of electronic components.

In this specification and the patent scope of the present invention, "aliphatic" refers to the relative concept to aromatic, and its definition refers to radicals, compounds, etc. that do not have aromatic properties. The "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same is true for the alkyl group in the alkoxy group. The "alkylene group" includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. A "halogenated alkyl group" is a group obtained by substituting part or all of the hydrogen atoms of an alkyl group with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. "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 substituted with fluorine atoms. "Structural unit" refers to the monomer unit that constitutes a polymer compound (resin, polymer, copolymer). When it is described as "may have a substituent" or "may have a substituent", it includes the case where a hydrogen atom (-H) is substituted with a monovalent group, and the case where a methylene group (-CH ₂ -) is substituted by a divalent group The situation is both. "Exposure" is a concept that includes the entire irradiation of radiation.

"Structural unit derived from hydroxystyrene" refers to the structural unit formed by breaking the ethylenic double bond of hydroxystyrene. "Structural unit derived from hydroxystyrene derivative" refers to the structural unit formed by breaking the ethylenic double bond of hydroxystyrene derivative. "Hydroxystyrene derivatives" refers to the concept of compounds in which the hydrogen atom at the α-position of hydroxystyrene is substituted with other substituents such as alkyl groups, halogenated alkyl groups, etc., and derivatives thereof. Examples of derivatives thereof include: hydroxystyrene in which the hydrogen atom at the α-position may be substituted with a substituent, and a compound in which the hydrogen atom of the hydroxyl group is substituted by an organic group; hydroxystyrene in which the hydrogen atom at the α-position may be substituted with a substituent. Compounds whose benzene ring is bonded with substituents other than hydroxyl groups; etc. Furthermore, unless otherwise specified, the α-position (α-position carbon atom) refers to the carbon atom to which the benzene ring is bonded. Examples of the substituent for the α-position hydrogen atom of substituted hydroxystyrene include the same substituents as those exemplified as the α-position substituent in the above-mentioned α-substituted acrylate.

The alkyl group as the α-position substituent is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, iso Propyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl), etc. Specific examples of the halogenated alkyl group as the α-position substituent include a group obtained by substituting a halogen atom for part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent”. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is particularly preferred. Specific examples of the hydroxyalkyl group as the α-position substituent include a group obtained by substituting a hydroxyl group for part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent”. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and is most preferably 1.

In this specification and the patent scope of the present invention, asymmetric carbon exists according to the structure shown in the chemical formula, and sometimes enantiomers and diastereomers may exist. In this case, These isomers are represented representatively by a formula. These isomers can be used individually or in the form of mixtures.

(Adhesive composition) The adhesive composition of the first aspect of the present invention can be used to form an adhesive layer that temporarily connects a semiconductor substrate or electronic device and a support that can transmit light. The adhesive composition of this form contains a polyurethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator (A). The above-mentioned polyurethane resin (P1) has a structural unit (u1) including a structure capable of absorbing at least part of light in the range of 300 to 800 nm wavelength.

＜Object to be temporarily connected＞ The adhesive composition of this embodiment can be used to form an adhesive layer that temporarily connects a semiconductor substrate or electronic device to a support. In this specification, "temporarily connected" means that the connected object is temporarily connected (for example, during any operation step). More specifically, in order to thin the device, transport the semiconductor substrate, mount the semiconductor substrate, etc., the semiconductor substrate or electronic device is temporarily adhered to the support and fixed (temporarily adhered) to the support. After the process is completed, , self-supporting body separation.

≪Semiconductor substrate≫ The semiconductor substrate to which the adhesive composition of the present embodiment is applied is not particularly limited, and it may be one generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is supplied to processes such as thinning and mounting while being supported by the support body. The semiconductor substrate may also be mounted with structures such as integrated circuits and metal bumps. As a semiconductor substrate, a silicon wafer substrate is typically exemplified, but it is not limited thereto. A ceramic substrate, a film substrate, a flexible substrate, etc. may also be used.

≪Electronic Devices≫ In this specification, "electronic device" refers to a component that constitutes at least a part of an electronic component. The electronic device is not particularly limited and may be one with various mechanical structures or circuits formed on the surface of the semiconductor substrate. The electronic device may preferably be a composite including a metal or semiconductor component and a resin that seals or insulates the component. The electronic device may be a rewiring layer described later and/or a semiconductor element or other element sealed or insulated by a sealing material or an insulating material, and may have a single-layer or multiple-layer structure.

≪Support≫ The support is a member that supports a semiconductor substrate or an electronic device. As will be described later, the support includes a member that has the property of transmitting light and supports the semiconductor substrate.

＜Polyurethane resin containing polymerizable carbon-carbon unsaturated bonds: (P1) component＞ The adhesive composition of this embodiment contains a polyurethane resin containing a polymerizable carbon-carbon unsaturated bond (hereinafter, also referred to as "(P1) component"). The component (P1) can be polymerized and hardened through polymerizable carbon-carbon unsaturated bonds to form an adhesive layer. Thereby, the semiconductor substrate or electronic device and the support can be temporarily connected. Furthermore, the urethane bond in component (P1) has a property of being decomposable by acid or alkali. Therefore, the above-mentioned adhesive layer can be easily removed by a treatment liquid containing acid or alkali. The component (P1) further has a structural unit (u1) including a structure capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm. Thereby, by irradiating the adhesive layer with light having a wavelength in the range of 300 to 800 nm, the structural unit (u1) absorbs the light and generates heat. Thereby, the adhesive layer can be modified.

The polymerizable carbon-carbon unsaturated bond contained in the component (P1) is not particularly limited, but it is preferably a radically polymerizable bond. The polymerizable carbon-carbon unsaturated bond may be a polymerizable carbon-carbon double bond or a polymerizable carbon-carbon triple bond, but is preferably a polymerizable carbon-carbon double bond. Examples of the polymerizable carbon-carbon unsaturated bond include a methacryloyl group and an acryloyl group. The number of polymerizable carbon-carbon unsaturated bonds contained in the component (P1) may be one type or two or more types. The equivalent of the polymerizable carbon-carbon unsaturated bond contained in the component (P1) is preferably 200 to 2000 g/eq., more preferably 300 to 1500 g/eq., and still more preferably 400 to 1200 g/eq. , the best value is 500~1000 g/eq. If the polymerizable carbon-carbon unsaturated bond equivalent is more than the lower limit of the above-mentioned preferred range, the elastic modulus, heat resistance, etc. of the adhesive layer will be further improved. When the polymerizable carbon-carbon unsaturated bond equivalent is equal to or less than the upper limit of the above-mentioned preferred range, the adhesive layer will not become excessively hard and the cleanability will be good. The above-mentioned equivalent number is the molecular weight of the polyurethane resin calculated per 1 equivalent of polymerizable carbon-carbon unsaturated bonds.

The weight average molecular weight (Mw) of the component (P1) is preferably 5,000 to 100,000, more preferably 1,000 to 50,000, further preferably 12,000 to 30,000, particularly preferably 13,000 to 25,000.

The component (P1) can be composed of a polyisocyanate compound (hereinafter, also referred to as "(I) component"), a polyol (hereinafter, also referred to as "(O) component"), and a compound from which the structural unit (u1) can be derived (Hereinafter, also referred to as "(U1) component") is synthesized by a polymerization addition reaction. It is preferable that at least one of the component (I) and the component (O) contains a polymerizable carbon-carbon unsaturated bond.

≪Polyisocyanate compound: (I) Component≫ In this specification, "polyisocyanate compound" refers to a compound (polyisocyanate) with two or more isocyanate groups (-N=C=O) or a compound with two or more blocked isocyanate groups. (Capped polyisocyanate). The polyisocyanate is not particularly limited, and polyisocyanates commonly used in the production of polyurethane resins can be used without particular limitations. Blocked polyisocyanate is a compound in which the isocyanate group of the polyisocyanate is blocked by reaction with a blocking agent and thereby deactivated. The blocked polyisocyanate used as component (I) is preferably one obtained by blocking isocyanate groups with a thermally dissociable blocking agent. Examples of thermally dissociable blocking agents include blocking agents such as oximes, diketones, phenols, and caprolactams. As for the blocked polyisocyanate obtained by using a thermally dissociable blocking agent, the isocyanate group is inactive at normal temperature. By heating, the thermally dissociable blocking agent is dissociated and the isocyanate group is regenerated.

Specific examples of the polyisocyanate include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone Alicyclic diisocyanates such as ketone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; and toluene diisocyanate Isocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, benzidine diisocyanate, terephthalene diisocyanate, naphthalene diisocyanate Isocyanates and other aromatic diisocyanates; and their biuret forms, isocyanurate forms, trimethylolpropane adducts, etc. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

Commercially available polyisocyanates can be used. Examples of commercially available polyisocyanates include Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, and Duranate MFA-75B. , Duranate MHG-80B, Duranate TUL-100, Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (the above are trade names, manufactured by Asahi Kasei Chemical Co., Ltd.), etc. One type of these products may be used alone, or two or more types may be used in combination.

Examples of the blocked isocyanate include compounds in which the isocyanate group of the above-mentioned polyisocyanate 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 is added to an isocyanate group and is stable at room temperature but is released when heated above the dissociation temperature to generate an isocyanate group. , known ones can be used without particular restrictions. Specific examples of the end-capping agent include, for example, lactam compounds such as γ-butyrolactamine, ε-caprolactam, γ-valerolactam, and propiolactam; methyl ethyl ketone Oxime compounds such as methyl isopentyl ketone oxime, methyl isobutyl ketone oxime, formamide oxime, acetamide oxime, acetone oxime, diethyl monooxime, benzophenone oxime, cyclohexanone oxime, etc. ; Monocyclic phenolic compounds such as phenol, cresol, catechol, and nitrophenol; Polycyclic phenolic compounds such as 1-naphthol; Methanol, ethanol, isopropyl alcohol, tert-butanol, trimethylolpropane, 2 -Alcohol compounds such as ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; alkyl malonate, dialkyl malonate, and acetic acid Active methylene compounds such as alkyl esters and acetyl acetone; etc. One type of end-capping agent may be used alone, or two or more types may be used in combination.

Blocked polyisocyanates can be produced by reacting polyisocyanates with blocking agents. The reaction between the polyisocyanate and the blocking agent is, for example, in a solvent without active hydrogen (1,4-dioxane, cellosolve acetate, etc.), under heating at about 50 to 100°C, and in the blocking process if necessary. Carry out in the presence of chemical catalyst. The usage ratio of polyisocyanate and blocking agent is not particularly limited. Based on the equivalent ratio of isocyanate groups in polyisocyanate to blocking agent, it is preferably 0.95:1.0～1.1:1.0, and more preferably 1:1.05～ 1.15. As the blocking catalyst, well-known ones can be used, for example, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenolate, and potassium methoxide; tetramethylammonium, tetraethylammonium, tetrabutylammonium, etc. Alkyl ammonium hydroxides; their organic weak acid salts such as acetate, octanoate, myristate, benzoate, etc.; and alkyl carboxylic acid bases such as acetic acid, caproic acid, caprylic acid, myristic acid, etc. Metal salts; etc. One type of blocking catalyst may be used alone, or two or more types may be used in combination.

Commercially available blocked polyisocyanates can 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 ( The above are trade names, manufactured by Asahi Kasei Co., Ltd.), etc.

As the component (I), a blocked polyisocyanate obtained by blocking an isocyanate group with a thermally dissociable blocking agent is preferred. (I) Component may be used individually by 1 type, and may be used in combination of 2 or more types. For example, a mixture of aliphatic diisocyanate and aromatic diisocyanate can be used as component (I). As the aliphatic diisocyanate, hydrogenated xylene diisocyanate is preferred. As the aromatic diisocyanate, 4,4-diphenylmethane diisocyanate is preferred.

≪Polyol: (O) component≫ Polyol ((O) component) is a compound having two or more hydroxyl groups (-OH). The polyol is not particularly limited, and polyols commonly used in the production of polyurethane resins can be used without particular limitations. Examples of the (O) component include polyols containing polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as "(O1) component") and other polyols (hereinafter also referred to as "(O2) )Element").

・Polyol containing polymerizable carbon-carbon unsaturated bonds ((O1) component) Examples of the component (O1) include a polyol containing at least one selected from the group consisting of a methacryloyl group and an acrylyl group. The component (O1) may have one polymerizable carbon-carbon unsaturated bond or two or more.

Examples of the component (O1) include esters of trivalent or higher polyhydric alcohols and methacrylic acid, acrylic acid, or derivatives thereof. As the above-mentioned trivalent or higher polyol, a trivalent or higher low molecular weight polyol is preferred. Examples of the above-mentioned trivalent or higher low molecular weight polyols include trivalent alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol; and pentavalent alcohols such as xylitol. ; 6-valent alcohols such as sorbitol, mannitol, allol, idbitol, galactitol, aldrose, inositol, and dipentaerythritol; 7-valent alcohols such as cyanodol; and 8-valent alcohols such as sucrose ;etc.

Specific examples of the component (O1) include glycerol mono(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, and bis(meth)acrylate. Glyceryl 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 includes methacrylate and acrylate, and refers to methacrylate or acrylate.

(O1) Component may be used individually by 1 type, or may be used in combination of 2 or more types. Among them, the (O1) component is preferably a glycol containing a methacryloyl group or an acrylyl group, and more preferably is glycerol mono(meth)acrylate or pentaerythritol di(meth)acrylate.

・Other polyols ((O2) component) The (O2) component is a polyol other than the above-mentioned (O1) component. The (O2) component is not particularly limited and may be an aliphatic polyol or an aromatic polyol. The (O2) component may be a low-molecular polyol (for example, a molecular weight of less than 500) or a high-molecular polyol (for example, a molecular weight of 500 or more).

Examples of low molecular weight polyols include: ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1, 5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkanediol with 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, alkane-1,2-diol with 17 to 20 carbon atoms, 1,3-cyclohexanedimethanol, 1, 4-Cyclohexane dimethanol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8 - Dihydric alcohols such as glycols and bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol; pentahydric alcohols such as xylitol; sorbose alcohol, mannitol, allol, idbitol, galactitol, aldrose, inositol, dipentaerythritol and other 6-valent alcohols; 7-valent alcohols such as cyanositol; and 8-valent alcohols such as sucrose; etc. . Among them, the low molecular weight polyol is preferably a dihydric alcohol (diol).

Examples of polymer polyols include phenol resins, resins containing a hydroxystyrene skeleton, polyester polyols, polyether polyols, polyetherester polyols, polyesteramide polyols, acrylic polyols, and polyols. Carbonate polyols, polyhydroxyalkanes, polyurethane polyols, and vegetable oil polyols, etc. The number average molecular weight of the polymer polyol is preferably 500 to 100,000.

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

[Phenolic resin] The phenol resin may be a novolac type phenol resin or a soluble phenolic type phenol resin. Novolac-type phenol resin can be obtained by addition-condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and aldehydes in the presence of an acid catalyst. Soluble phenol-formaldehyde phenol resin can be obtained by the addition and condensation of phenols and aldehydes under an alkali catalyst.

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

Examples of the aldehydes include formaldehyde, paraformaldehyde, trimaldehyde, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, and o-hydroxybenzaldehyde. , m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic aldehyde, 4-iso Propylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenylbenzaldehyde, etc.

The acid catalyst used in the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. can be used. The alkali catalyst used in the addition condensation reaction is not particularly limited, and sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, triethylamine, sodium carbonate, hexamethylenetetramine, etc. can be used.

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

[Chemical 1] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or a divalent linking base. Wa ^x1 is an aromatic hydrocarbon group with a valence of (n _ax1 +1). n _ax1 is an integer from 1 to 3]

In the above formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include methyl, ethyl, propyl, and isopropyl. base, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The haloalkyl group having 1 to 5 carbon atoms in R is a group obtained by substituting part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is 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. From the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.

In the above formula (a10-1), Ya ^x1 is a single bond or a divalent linking group. Suitable examples of the divalent linking group in Ya ^x1 include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom.

・Divalent hydrocarbon group which may have a substituent: When Ya ^x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

・・The aliphatic hydrocarbon group in Ya ^x1 refers to a non-aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and is generally preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

・・・Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, and still more preferably a carbon number of 1 to 4, preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specific examples thereof include methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], 1,3-propylene [-(CH ₂ ) ₃ -], 1,4-butylene [-(CH ₂ ) ₄ -], 1,5-pentylene [-(CH ₂ ) ₅ -] wait. The number of carbon atoms of the branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - and other alkyl methylenes Base; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -alkyl ethylidene; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -alkyl trimethylene; -CH( CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - and other alkyl groups such as tetramethylene and other alkyl alkylene groups. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

The above-mentioned linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

・・・Aliphatic hydrocarbon group containing ring in the structure Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group containing a heteroatom in the ring structure that may contain a substituent (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), The above-mentioned cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the above-mentioned cyclic aliphatic hydrocarbon group is intermediate between the linear or branched aliphatic hydrocarbon group. Key et al. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above. The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocyclic alkane is preferred. The monocyclic alkane is preferably a monocyclic alkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane (polycycloalkane), and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. , specific examples include adamantane, nordecane, isoxane, tricyclodecane, tetracyclododecane, and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and the like. Regarding the alkyl group as the above-mentioned substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferred. The alkoxy group as the above substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, The third butoxy group is preferably methoxy or ethoxy. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred. Examples of the halogenated alkyl group as the above-mentioned substituent include a group in which part or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned halogen atoms. As for the cyclic aliphatic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom. As the heteroatom-containing substituent, -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O- are preferred.

・・The aromatic hydrocarbon group in Ya ^x1 is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be a single ring or a polycyclic ring. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Wherein, 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 heterocycles obtained by substituting part of the carbon atoms constituting the aromatic hydrocarbon rings with heteroatoms; and the like. Examples of heteroatoms in the aromatic heterocyclic ring include oxygen atoms, sulfur atoms, nitrogen atoms, and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring, a thiophene ring, and the like. Specific examples of the aromatic hydrocarbon group include: a group obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); including two or more A group obtained by removing 2 hydrogen atoms from aromatic compounds with an aromatic ring (such as biphenyl, fluorine, etc.); a group obtained by removing 1 hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl or Heteroaryl) A group in which one hydrogen atom is substituted by an alkylene group (for example, from benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthyl) A group obtained by further removing one hydrogen atom from the aryl group in an arylalkyl group such as ethyl), etc. The number of carbon atoms of the alkylene group bonded to the above-mentioned aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Regarding the above-mentioned aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted by a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted by a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and the like. Regarding the alkyl group as the above-mentioned substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is most preferred. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include groups exemplified as substituents for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

・Bivalent linking group containing a hetero atom: When Ya ^x1 is a divalent linking group containing a hetero atom, preferred examples of the linking group include: -O-, -C(=O) -O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H can pass through alkane (substituted with substituents such as hydroxyl group and hydroxyl group), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, 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 - The group represented by OC(=O)-Y ²² -or-Y ²¹ -S(=O) ₂ -OY ²² - [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, m'' is an integer from 0 to 3], etc. The above divalent linking groups containing heteroatoms are -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)-. In this case, its H may be substituted by substituents such as alkyl group and acyl group. The number of carbon atoms of the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, 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 -, Y ²¹ and Y ²² are independently It is a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same divalent hydrocarbon groups as those exemplified in the description of the divalent linking group (a divalent hydrocarbon group which may have a substituent). Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, further preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably methylene base or ethyl group. Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylidene group or an alkyl methylene group. The alkyl group in the alkyl methylene 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 is a methyl group. In the basis represented by the formula -[Y ²¹ -C(=O)-O] _m'' -Y ²² -, m'' is an integer from 0 to 3, preferably an integer from 0 to 2, and more preferably 0 Or 1, the best is 1. That is, as the group represented by the formula -[Y ²¹ -C(=O)-O] _m'' -Y ²² -, a group represented by the formula -Y ²¹ -C(=O)-OY ²² - is particularly preferred. . Among them, a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferred. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1.

As Ya ^x1 , a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), -C(=O)-NH-, a linear or branched chain is preferred. Alkylene group, or a combination thereof, of which a single bond is particularly preferred.

In the above formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group with a valence of (n _ax1 +1). Examples of the aromatic hydrocarbon group in Wa ^x1 include a group obtained by removing (n _ax1 +1) hydrogen atoms from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be a single ring or a polycyclic ring. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles obtained by substituting part of the carbon atoms constituting the aromatic hydrocarbon rings with heteroatoms; and the like. Examples of heteroatoms in the aromatic heterocyclic ring include oxygen atoms, sulfur atoms, nitrogen atoms, and the like. Specific examples of the aromatic heterocyclic ring include a pyridine ring, a thiophene ring, and the like.

In the above formula (a10-1), n _ax1 is an integer from 1 to 3, preferably 1 or 2, more preferably 1.

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

[Chemicalization 2]

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

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

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

[Chemical 3] [In the formula, Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. np is an integer above 2]

In the above general formula (PC-1), Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. The above divalent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of the divalent hydrocarbon group include the same divalent hydrocarbon groups as those exemplified for Ya ^x1 in the general formula (a10-1). The divalent hydrocarbon group in Rp ¹ and Rp ² 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. Specific examples of Rp ¹ and Rp ² include -(CH ₂ ) ₆ - or -(CH ₂ ) ₅ -.

The weight average molecular weight (Mw) of the polycarbonate polyol is preferably 500 to 5000, more preferably 500 to 3000, further preferably 500 to 2000, particularly preferably 500 to 1000.

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

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

Examples of the polyether polyol include a mixture of alkylene oxide compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran with water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, etc. Polyether polyols obtained by polymerizing low-weight polyols as initiators.

Examples of the polyetherester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, dialkyl esters thereof, or the like. Polyetherester polyol obtained by reacting the mixture with the above-mentioned polyether polyol.

Examples of the polyesteramide polyol include those obtained by combining aliphatic diamines having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine, etc. as raw materials during the above-mentioned esterification reaction. Polyesteramide polyol.

Examples of the acrylic polyol include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, and the like. For example, polyesteramide polyol obtained by copolymerization of acrylic acid, methacrylic acid or their esters.

Examples of polyhydroxyalkanes include liquid rubber obtained by copolymerizing butadiene or butadiene and acrylamide.

The polyurethane polyol is a polyol having one or more urethane bonds per molecule. Examples thereof include polyether polyols, polyester polyols, and polyether polyols having a number average molecular weight of 200 to 20,000. Polyurethane polyol obtained by reacting ester polyol, etc. with polyisocyanate under conditions such that NCO/OH is preferably less than 1, more preferably 0.9 or less.

Examples of the vegetable oil-based polyol include castor oil, castor oil-modified polyol, dimer acid-modified polyol, and soybean oil-modified polyol. Among these, as the vegetable oil-based polyol, a castor oil-modified polyol is preferred, and a castor oil-modified diol is 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 It is 0.3-3, and it is more preferable that it is 0.4-2.5.

(O2) component may be used individually by 1 type, and may be used in combination of 2 or more types. Among the above, as the (O2) component, from the viewpoint of adjusting the viscosity of the adhesive composition and the hardness of the adhesive layer, polycarbonate polyols and low molecular polyols are preferred. In addition, from the viewpoint of improving the heat resistance of the adhesive layer, castor oil-modified polyol can be used as the (O2) component.

As the (O) component, from the viewpoint of adjusting the viscosity of the adhesive composition, the heat resistance of the adhesive layer, etc., a combination of the (O1) component and the (O2) component is preferred. As the above-mentioned (O2) component, a low molecular weight polyol, a polycarbonate polyol, a castor oil modified polyol, or a combination thereof is preferred. Specific examples of the (O2) component combined with the (O1) component include: a combination of polycarbonate polyol, castor oil-modified polyol, and low molecular polyol; polycarbonate polyol, and castor oil. Combinations of modified polyols; and polycarbonate polyols, etc. The mass ratio between (O1) component and (O2) component is preferably (O1): (O2)=1:5～5:1, more preferably 1:4～2:1, further preferably 1:4～1 :1, the best value is 1:4~1:2. By setting the mass ratio of the (O1) component to the (O2) component within the above range, the elastic modulus, heat resistance, etc. of the adhesive layer can be improved.

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

≪Compounds from which structural unit (u1) can be derived: (U1) component≫ The component (U1) is a compound containing a structure capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm. The component (U1) is preferably a polyisocyanate compound or polyol. That is, the (U1) component may be contained in the said (I) component or (O) component. The component (U1) is preferably a polyol. When the component (U1) is a polyol, the component (U1) may be the component (O1) or the component (O2).

The component (U1) contains a structure capable of absorbing light in the wavelength range of 300 to 800 nm (hereinafter, also referred to as "structure X"). Therefore, structural unit (u1) derived from component (U1) also includes structure X. In the component (P1), the structure X functions as a light-absorbing group capable of absorbing light with a wavelength of 300 to 800 nm. Structure The structure It can absorb light in the wavelength range of 300 to 400 nm. Structure X preferably has an absorption peak in the above wavelength range. For the structure

The structure The aromatic condensed ring skeleton contains a condensed ring having at least one aromatic ring. The above-mentioned aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings in the condensed ring is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and particularly preferably 2 or 3. The condensed ring may be composed only of an aromatic ring, or may be a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, but is preferably a condensed ring composed only of an aromatic ring. Specific examples of the condensed ring include naphthalene, anthracene, phenanthrene, pyrene, and the like. Among them, anthracene or phenanthrene is preferred.

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

[Chemical 4] [In the formula (u1-1), X ¹ is an n1 valent group containing a structure capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm; Y ¹ is a divalent linking group, and n1 is an integer from 2 to 4. The plural Y ^1's may be the same as or different from each other. In the formula (u1-2), X ² is a 1-valent group containing a structure that can absorb at least part of the light in the wavelength range of 300 to 800 nm; Y ² is a 3-valent linking group; Y ³ is an n2-valent linking group; n2 It is an integer between 2 and 4. A plurality of X ² may be the same as or different from each other. A plurality of Y ² may be the same or different from each other]

In the general formula (u1-1), Y ¹ is a divalent linking group. In the general formula (u1-2), Y ² is a trivalent linking group. Examples of the divalent or trivalent linking group include a hydrocarbon group which may have a substituent. The above-mentioned hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group mentioned above may be saturated or unsaturated, but is preferably saturated. The above-mentioned aliphatic hydrocarbon group may be linear or branched, or may include a ring in the structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably has 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. The aliphatic hydrocarbon group mentioned above may have a substituent. The above-mentioned substituent may be a substituent that substitutes a hydrogen atom or a substituent that substitutes a methylene group (-CH ₂ -) in the carbon chain. Examples of the substituent for substituting a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, and the like, and a hydroxyl group or an amino group is preferred. Examples of the substituent for substituting the methylene group (-CH ₂ -) in the carbon chain include -O-, -CO-, -NH-, -COO-, -CONH-, and the like.

The above-mentioned aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the above-mentioned aromatic hydrocarbon group may be a single ring or a polycyclic ring. The above-mentioned aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring and an aliphatic hydrocarbon group are connected. The above aromatic hydrocarbon group may have a substituent. The above substituent may be a substituent that substitutes a hydrogen atom of the aromatic ring, or a substituent that substitutes a hetero atom with a carbon atom constituting the aromatic ring. Examples of the substituent for substituting a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, and the like, and a hydroxyl group or an amino group is preferred. Examples of the hetero atom that substitutes the aromatic ring include a nitrogen atom, an oxygen atom, a sulfur atom, and the like, and a nitrogen atom is preferred.

In the general formula (u1-2), Y ³ is an n2-valent linking group. Examples of Y ³ include a hydrocarbon group which may have a substituent. The above-mentioned hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group mentioned above may be saturated or unsaturated, but is preferably saturated. The above-mentioned aliphatic hydrocarbon group may be linear or branched, or may include a ring in the structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably has 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. The aliphatic hydrocarbon group may or may not have a substituent. The above-mentioned substituent may be a substituent that substitutes a hydrogen atom or a substituent that substitutes a methylene group (-CH ₂ -) in the carbon chain. Examples of the substituent for substituting a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, and the like, and a hydroxyl group or an amino group is preferred. Examples of the substituent for substituting the methylene group (-CH ₂ -) in the carbon chain include -O-, -CO-, -NH-, -COO-, -CONH-, and the like.

The above-mentioned aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the above-mentioned aromatic hydrocarbon group may be a single ring or a polycyclic ring. The above-mentioned aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring and an aliphatic hydrocarbon group are connected. The above aromatic hydrocarbon group may have a substituent. The above substituent may be a substituent that substitutes a hydrogen atom of the aromatic ring, or a substituent that substitutes a hetero atom with a carbon atom constituting the aromatic ring. Examples of the substituent for substituting a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, and the like, and a hydroxyl group or an amino group is preferred. Examples of the hetero atom that substitutes the aromatic ring include a nitrogen atom, an oxygen atom, a sulfur atom, and the like, and a nitrogen atom is preferred.

Y ³ is preferably an aliphatic hydrocarbon group which may have a substituent, more preferably a saturated aliphatic hydrocarbon group which may have a substituent, further preferably a saturated aliphatic hydrocarbon group which does not have a substituent, and is particularly preferably linear or branched. The alkyl group. The number of carbon atoms of the above-mentioned alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, particularly preferably 1 to 3, or 1 or 2.

In the general formula (u1-1), X ¹ is the n 1 valence group containing a structure (structure X) that can absorb at least part of the light in the range of 300 to 800 nm wavelength. Examples of X ¹ include groups containing an aromatic condensed ring skeleton, a benzophenone skeleton, a benzoylmethane skeleton, a benzoylbenzene skeleton, or a benzotriazole skeleton. n valence base. In the general formula (u1-2), X ² is a valence group containing a structure (structure X) capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm. Examples of X ² include groups containing an aromatic condensed ring skeleton, a benzophenone skeleton, a benzoylmethane skeleton, a benzoylbenzene skeleton, or a benzotriazole skeleton. 1 price base.

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

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

[Chemistry 5] [In ^Formula ( ^{u1-1-1 )} , Or branched alkyl group; n1 is an integer from 2 to 4. A plurality of Y ¹¹ may be the same as or different from each other. The plural L ¹¹ may be the same as or different from each other. In the formula (u1-2-1), X ² is a univalent group containing a structure that can absorb at least part of the light in the wavelength range of 300 to 800 nm; Y ²¹ is a trivalent linking group; L ²¹ is a linear or Branched alkyl group; Y ³ is an n2-valent linking group; n2 is an integer from 2 to 4. A plurality of X ² may be the same as or different from each other. The plural Y ²¹ may be the same as or different from each other. Plural L ²¹ may be the same or different from each other]

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

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

X ¹ , X ² , n1, n2, and Y ³ in the general formulas (u1-1-1) and (u1-2-1) are the same as X ¹ in the above formulas (u1-1) and (u1-2) , X ² , n1, n2, and Y ³ are respectively the same.

Examples of X ¹ or X ² containing an aromatic condensed ring skeleton include those represented by the following general formula (Xa-1) or (Xa-2). In the case of X ¹ , n in the general formula (Xa-1) or (Xa-2) is an integer from 2 to 4, preferably 2. In the case of X ² , n in the general formula (Xa-1) or (Xa-2) is 1.

[Chemical 6] [In the formula, L ^a1 and L ^a2 each independently represent a single bond or a divalent linking group, and R ^a1 and R ^a2 each independently represent a substituent. n represents an integer from 1 to 4. m represents an integer from 0 to 9, m+n≤10. When n is 2 or more, there are plural L ^a1 and L ^a2 which may be the same or different from each other. When m is 2 or more, there are plural R ^a1 and R ^a2 which may be the same or different from each other. * is the bonding key]

In the general formulas (Xa-1) and (Xa-2), L ^a1 and L ^a2 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include a hydrocarbon group which may have a substituent. The above-mentioned hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group mentioned above may be saturated or unsaturated, but is preferably saturated. The above-mentioned aliphatic hydrocarbon group may be linear or branched, or may include a ring in the structure. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably has 1 to 3 carbon atoms. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. The aliphatic hydrocarbon group mentioned above may have a substituent. The above-mentioned substituent may be a substituent that substitutes a hydrogen atom or a substituent that substitutes a methylene group (-CH ₂ -) in the carbon chain. Examples of the substituent for substituting a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, and the like, and a hydroxyl group or an amino group is preferred. Examples of the substituent for substituting the methylene group (-CH ₂ -) in the carbon chain include -O-, -CO-, -NH-, -COO-, -CONH-, and the like.

The above-mentioned aromatic hydrocarbon group is a hydrocarbon group containing at least one aromatic ring. The aromatic ring contained in the above-mentioned aromatic hydrocarbon group may be a single ring or a polycyclic ring. The above-mentioned aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of aromatic rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2. The aromatic hydrocarbon group may be a group in which an aromatic ring and an aliphatic hydrocarbon group are connected. The above aromatic hydrocarbon group may have a substituent. The above substituent may be a substituent that substitutes a hydrogen atom of the aromatic ring, or a substituent that substitutes a hetero atom with a carbon atom constituting the aromatic ring. Examples of the substituent for substituting a hydrogen atom include a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, and the like, and a hydroxyl group or an amino group is preferred. Examples of the hetero atom that substitutes the aromatic ring include a nitrogen atom, an oxygen atom, a sulfur atom, and the like, and a nitrogen atom is preferred.

In the general formulas (Xa-1) and (Xa-2), R ^a1 and R ^a2 each independently represent a substituent. Examples of R ^a1 and R ^a2 include an alkyl group, a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxyl group, a cyano group, a nitrile group, a nitrile alkyl group, an alicyclic group, and the like. The alkyl group, alkoxy group and nitrilealkyl group preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. The alicyclic group preferably has 1 to 6 carbon atoms. Examples of the nitrile alkyl group include a malononitrile group. The alicyclic group may be an alicyclic hydrocarbon ring or an alicyclic heterocyclic ring. Examples of the alicyclic heterocyclic ring include an alicyclic heterocyclic ring containing a sulfur atom, a nitrogen atom, or an oxygen atom. Specific examples of alicyclic heterocyclic rings include dithiolane.

In general formulas (Xa-1) and (Xa-2), m represents an integer from 0 to 9. m is preferably 0 to 6, more preferably 0 to 5, further preferably 0 to 3, particularly preferably 0 to 2. m and n have the relationship of m+n≤10.

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

[Chemical 7] [In the formula, L ^b1 and L ^b2 each independently represent a single bond or a divalent linking group, and R ^b1 and R ^b2 each independently represent a substituent. p and q each independently represent an integer from 0 to 4. m1 and m2 each independently represent an integer from 0 to 5, m1+p≤5, m2+q≤5. When p is 2 or more, there are a plurality of L ^b1 which may be the same or different from each other. When q is 2 or more, there are plural L ^b2 which may be the same or different from each other. When m1 is 2 or more, there are a plurality of R ^b1 which may be the same or different from each other. When m2 is 2 or more, there are a plurality of R ^b2 which may be the same or different from each other. * is the bonding key]

In the general formula (Xb), L ^b1 and L ^b2 each independently represent a single bond or a divalent linking group. Examples of the divalent connecting group include the same connecting groups as those exemplified for L ^a1 and L ^a2 in the above formulas (Xa-1) and (Xa-2). L ^b1 and L ^b2 are preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, and preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group, or a part of the methylene group (-CH ₂ -) constituting the carbon chain is substituted by -O-, -CO-, -NH-, -COO-, -CONH -Substituted alkyl.

In the general formula (Xb), R ^b1 and R ^b2 each independently represent a substituent. Examples of R ^b1 and R ^b2 include the same substituents as those exemplified for R ^a1 and R ^a2 in the above formulas (Xa-1) and (Xa-2).

In the general formula (Xb), m1 and m2 each independently represent an integer from 0 to 5, m1+p≤5, m2+q≤5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.

Examples of X ¹ or X ² having a benzylmethane skeleton include those represented by the following general formula (Xc). In the case of X ¹ , p+q in the general formula (Xc) is an integer from 2 to 4, preferably 2. In the case of X ² , p+q in the general formula (Xc) is 1.

[Chemical 8] [In the formula, L ^c1 and L ^c2 each independently represent a single bond or a divalent linking group, and R ^c1 and R ^c2 each independently represent a substituent. p and q each independently represent an integer from 0 to 4. m1 and m2 each independently represent an integer from 0 to 5, m1+p≤5, m2+q≤5. When p is 2 or more, there are a plurality of L ^c1 which may be the same or different from each other. When q is 2 or more, there are a plurality of L ^c2 which may be the same or different from each other. When m1 is 2 or more, there are a plurality of R ^c1 which may be the same or different from each other. When m2 is 2 or more, there are a plurality of R ^c2 which may be the same or different from each other. * is the bonding key]

In the general formula (Xc), L ^c1 and L ^c2 each independently represent a single bond or a divalent linking group. Examples of the divalent connecting group include the same connecting groups as those exemplified for L ^a1 and L ^a2 in the above formulas (Xa-1) and (Xa-2). L ^c1 and L ^c2 are preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, and preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group, or a part of the methylene group (-CH ₂ -) constituting the carbon chain is substituted by -O-, -CO-, -NH-, -COO-, -CONH -Substituted alkyl.

In the general formula (Xc), R ^c1 and R ^c2 each independently represent a substituent. Examples of R ^c1 and R ^c2 include the same substituents as those exemplified for R ^a1 and R ^a2 in the above formulas (Xa-1) and (Xa-2).

In the general formula (Xc), m1 and m2 each independently represent an integer from 0 to 5, m1+p≤5, m2+q≤5. m1 and m2 are preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1.

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

[Chemical 9] [In the formula, L ^d1 , L ^d2 and L ^d3 each independently represent a single bond or a divalent linking group, and R ^d1 , R ^d2 and R ^d3 each independently represent a substituent. p, q and r each independently represent an integer from 0 to 4. m1 and m2 each independently represent an integer from 0 to 5, m3 represents an integer from 1 to 4, m1+p≤5, m2+q≤5, m3+r=4. When p is 2 or more, there are a plurality of L ^d1 which may be the same or different from each other. When q is 2 or more, there are a plurality of L ^d2 which may be the same or different from each other. When r is 2 or more, there are a plurality of L ^d3 which may be the same or different from each other. When m1 is 2 or more, there are a plurality of R ^d1 which may be the same or different from each other. When m2 is 2 or more, there are a plurality of R ^d2 which may be the same or different from each other. When m3 is 2 or more, there are a plurality of R ^d3 which may be the same or different from each other. * is the bonding key]

In the general formula (Xd), L ^d1 , L ^d2 and L ^d3 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include the same divalent linking groups as those exemplified for L ^a1 and L ^a2 in the above formulas (Xa-1) and (Xa-2). L ^d1 , L ^d2 and L ^d3 are preferably a single bond or an aliphatic hydrocarbon group which may have a substituent, and more preferably a single bond or an alkyl group which may have a substituent. The alkyl group which may have a substituent preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. The alkyl group which may have a substituent is preferably an alkyl group, or a part of the methylene group (-CH ₂ -) constituting the carbon chain is substituted by -O-, -CO-, -NH-, -COO-, -CONH -Substituted alkyl.

In the general formula (Xd), R ^d1 , R ^d2 and R ^d3 each independently represent a substituent. Examples of R ^d1 , R ^d2 and R ^d3 include the same substituents as those exemplified for R ^a1 and R ^a2 in the above formulas (Xa-1) and (Xa-2).

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

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

[Chemical 10] [In the formula, L ^e represents a single bond or a divalent linking group, and R ^e represents a substituent. n represents an integer from 0 to 4. m represents an integer from 0 to 4, m+n≤5. When n is 2 or more, there are plural L ^e which may be the same or different from each other. When m is 2 or more, there are plural R ^e which may be the same or different from each other. * is the bonding key]

In the general formula (Xe), L ^e represents a single bond or a divalent linking group. Examples of the divalent connecting group include the same connecting groups as those exemplified for L ^a1 and L ^a2 in the above formulas (Xa-1) and (Xa-2). L ^e is preferably a single bond or a hydrocarbon group that may have a substituent, preferably a single bond, an alkyl group that may have a substituent, or a group in which one hydrogen atom of the benzene ring is substituted with an alkyl group. As the alkyl group which may have a substituent and the alkyl group bonded to a benzene ring, it is preferable that it has 1-5 carbon atoms, and it is more preferable that it has 1-3 carbon atoms.

In the general formula (Xe), R ^e represents a substituent. As R ^e , the same substituents as those exemplified for R ^a1 and R ^a2 in the above formulas (Xa-1) and (Xa-2) can be exemplified.

In the general formula (Xe), m represents an integer from 0 to 4. m is preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 or 1. m and n have the relationship m+n≤5.

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

[Chemical 11]

(U1) The component may be used individually by 1 type, or may be used in combination of 2 or more types. The ratio of the component (U1) to all the monomers used to synthesize the component (P1) can be, for example, 10 mass% or more, 15 mass% or more, or 100 mass% or more based on the mass of all the monomers (100 mass%). More than 20% by mass. If the ratio of the component (U1) is equal to or higher than the above-mentioned preferable lower limit, the separation performance will be good. The ratio of component (U1) to all monomers used to synthesize component (P1) is, for example, 70 mass% or less, 65 mass% or less, or 60 mass% relative to the mass of all monomers (100 mass%). or less, 55 mass% or less, or 50 mass% or less. If the ratio of the component (U1) is less than the above-mentioned preferable upper limit, balance with other monomers can be easily achieved.

The component (P1) can be synthesized by mixing the component (I), the component (O), and the component (U1), and copolymerizing them according to a known synthesis method of polyurethane resin. The copolymerization of component (I) and component (O) is preferably carried out in the presence of a known urethanation catalyst such as a bismuth catalyst. In addition, in order to avoid the polymerization of the polymerizable carbon-carbon unsaturated bond in the component (O1), a polymerization inhibitor may be added to the reaction system. (O) component preferably contains (O1) component and (O2) component. The component (U1) is preferably added as the component (O), more preferably added as the component (O2).

(P1) A component may be used individually by 1 type, or 2 or more types may be used together. The content of the component (P1) in the adhesive composition of this embodiment is not particularly limited as long as it is a concentration that can be applied to a support or the like. The content of the component (P1) in the adhesive composition is preferably 10 to 60 mass%, more preferably 20 to 60 mass%, and still more preferably 10 to 60 mass% relative to the total amount of the adhesive composition (100 mass%). It is 30~60% by mass.

≪Polymerization initiator: (A) component≫ The adhesive composition of this embodiment contains a polymerization initiator (hereinafter, also referred to as (A) component). Polymerization initiator refers to a component that has the function of promoting polymerization reaction. Examples of the component (A) include thermal polymerization initiators, photopolymerization initiators, and the like.

Examples of the thermal polymerization initiator include peroxides, azo polymerization initiators, and the like.

Examples of the peroxide in the thermal polymerization initiator include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, and peroxyester. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butylcumyl peroxide, propyl peroxide, and peroxide. Benzyl oxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-chlorobenzoyl peroxide -Bromomethylbenzoyl peroxide, lauryl peroxide, potassium persulfate, diisopropyl percarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl peroxytriphenylacetate, tert-butyl hydroperoxide, tert-butyl peroxyformate, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butyl peroxyphenylacetate Tributyl ester, tert-butyl peroxy 4-methoxyacetate, tert-butyl peroxy N-(3-toluyl)carbamate, etc.

Among the above-mentioned peroxides, for example, the trade names "Percumyl (registered trademark)", the trade name "Perbutyl (registered trademark)", the trade name "Peroyl (registered trademark)" and the trade name "" manufactured by Nippon Oils and Fats Co., Ltd. can be used Perocta (registered trademark)" and other commercial products.

Examples of the azo polymerization initiator among the 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-amino) Propane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, 2,2'-azo Methyl bis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2' -Dimethylazobisisobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sodium sulfonate), 2-(4-methylphenylazo)-2-methyl 4,4'-Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 2,2'-azobis -2-Methylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid dimethyl ester, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1' -Azobiscyclohexanenitrile, 2,2'-Azobis-2-propylbutanenitrile, 1,1'-Azobiscyclohexanenitrile, 2,2'-Azobis-2-propylbutanenitrile, 1,1'-Azobis-1-chlorophenylethane, 1,1'-Azobis-1-cyclohexanecarbonitrile, 1,1'-Azobis-1-cycloheptanenitrile, 1 ,1'-azobis-1-phenylethane, 1,1'-azobiscumyl, 4-nitrophenylazobenzylcyanoacetate ethyl ester, phenylazodiphenyl Methane, phenylazobistriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly(bisphenol A-4 , 4'-azobis-4-cyanovalerate), poly(tetraethylene glycol-2,2'-azobisisobutyrate), etc.

Examples of the photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxy Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one , bis(4-dimethylaminophenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl -2-Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, ethanone 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-1-(o-acetyl oxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'- Methyl dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Butyl formate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl ketal, benzene Dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime, methyl o-phenyl benzoate, 2,4-diethyl 9-oxysulfur𠮿 , 2-chloro-9-oxosulfide𠮿 , 2,4-dimethyl 9-oxosulfide𠮿 , 1-Chloro-4-propoxy 9-oxysulfide𠮿 , sulfur , 2-chlorosulfur𠮿 ,2,4-diethylsulfide𠮿 , 2-methylsulfide𠮿 , 2-isopropylsulfide𠮿 , 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, isopropyl peroxide Benzene, 2-mercaptobenzimidazole, 2-mercaptobenzoethazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer Phenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl) base)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer , benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., Michelone), 4,4'-bisdiethylaminobis Benzophenone (i.e., ethyl Michelinone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoyl, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin third butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylphenyl ether Ketone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichlorobenzene Ethyl ketone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, 9-oxosulfide𠮿 , 2-Methyl 9-oxosulfide𠮿 , 2-isopropyl 9-oxosulfide𠮿 , dibenzocycloheptanone, 4-dimethylaminobenzoate amyl ester, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-( 9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytristrimethoxy, 2,4,6-tris(trichloromethyl)symmetric trisaccharide, 2- Methyl-4,6-bis(trichloromethyl) symmetry, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetry Tris𠯤, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)symmetric tris𠯤, 2-[2-(4-diethylamino-2- Methylphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric triethyl, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis (Trichloromethyl) symmetric tris- 4,6-bis (trichloromethyl) symmetric tris, 2-(4-n-butoxyphenyl)-4,6-bis (trichloromethyl) symmetric tris, 2,4-bis-tri Chloromethyl-6-(3-bromo-4-methoxy)phenyl symmetry, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl symmetry Tris, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl symmetric tris, 2,4-bis-trichloromethyl-6-( 2-Bromo-4-methoxy) styrylphenyl symmetric three 𠯤 etc.

Among the above-mentioned photopolymerization initiators, for example, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (all trade names, manufactured by BASF Corporation) and "NCI- 831" (trade name, manufactured by ADEKA Co., Ltd.) and other commercial products.

(A) Component may be used individually by 1 type, and may be used in combination of 2 or more types. As component (A), a thermal polymerization initiator is preferred, and a peroxide is more preferred. The usage amount of component (A) can be adjusted according to the usage amount of component (P1). The content of the polymerization initiator in the adhesive composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the component (P1).

＜Optional ingredients＞ In addition to the above-mentioned components, the adhesive composition of this embodiment may contain any component within the range which does not impair the effect of this invention. The arbitrary components are not particularly limited, and examples thereof include polymerization inhibitors, solvent components, plasticizers, adhesive auxiliaries, stabilizers, colorants, surfactants, and the like.

≪Polymerization inhibitor≫ Polymerization inhibitors refer to components that have the function of preventing radical polymerization caused by heat or light. Polymerization inhibitors show high reactivity towards free radicals.

As a polymerization inhibitor, one having a phenolic skeleton is preferred. For example, hindered phenol-based antioxidants can be used as such polymerization inhibitors, and examples thereof include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, and methyl p- Hydroquinone, pentoquinone, pentoxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylene)bis(2-methyl) Phenol), 4,4'-(1-methylethylene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl) -1-Methylethyl)phenyl]ethylene]bisphenol, 4,4',4''-ethylene tris(2-methylphenol), 4,4',4''-ethylene Triphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2 ,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(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)propionate, n-octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl)isocyanurate acid ester, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.

One type of polymerization inhibitor may be used alone, or two or more types may be used in combination. The content of the polymerization inhibitor can be appropriately determined depending on the type of the resin component, the purpose of the adhesive composition, and the use environment.

≪Surfactant≫ The adhesive composition of this embodiment can be prepared by dissolving (P1) component, (A) component, and optional optional components in a solvent component and mixing them. As the solvent component, one capable of dissolving each of the above components can be used.

Examples of the solvent component include hydrocarbon solvents, petroleum solvents, and other solvents other than the above solvents. Hereinafter, hydrocarbon solvents and petroleum solvents are also collectively referred to as "(S1) component". Solvent components other than the (S1) component are also called "(S2) components".

Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons. Examples of the hydrocarbon solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; isooctane , isononane, isododecane and other branched-chain hydrocarbons; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, 𦯉 Alkane, norpine, pinane, thujaane, carane, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene , α-thujone, β-thujone, cyclohexane, cycloheptane, cyclooctane and other alicyclic hydrocarbons; toluene, xylene, indene, pentacyclopentadiene, indane, tetrahydroindene, Aromatic hydrocarbons such as naphthalene, tetralin (tetralin), and decalin (decalin).

Petroleum-based solvents refer to solvents obtained by refining heavy oil, and examples thereof include white kerosene, paraffin-based solvents, and isoparaffin-based solvents.

Examples of the component (S2) include terpene solvents having polar groups such as oxygen atoms, carbonyl groups or acetyloxy groups. Examples include geraniol, nerol, linalol, citral, and citronellol. , menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydrorosinol Acetate, 1,4-cineole, 1,8-cineole, borneol, cyperone, ionone, thujone, camphor, etc.

Moreover, as the (S2) component, lactones such as γ-butyrolactone, acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-amyl ketone, and methyl isopentyl can also be exemplified. Ketones such as ketone and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, and propylene glycol monoacetate. , or compounds with ester bonds such as dipropylene glycol monoacetate, monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of the above-mentioned polyols or compounds with ester bonds. Derivatives of polyols such as compounds with ether bonds (among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as diethane Class; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxyethyl propionate and other esters ; Aromatic organic solvents such as anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butyl phenyl ether.

A solvent component may be used individually by 1 type, and may be used in combination of 2 or more types. As the solvent component, a solvent component that is inert to the component (P1) is preferred. Preferable solvent components include, for example, ester solvents, ketone solvents, aromatic hydrocarbon solvents, PGMEA, PGME, and mixed solvents thereof.

The content of the solvent component in the adhesive composition of this embodiment may be appropriately adjusted according to the thickness of the adhesive composition layer. The content of the solvent component is preferably in the range of 40 to 90 mass % with respect to the total amount of the adhesive composition (100 mass %), for example. That is, in the adhesive composition of this embodiment, the solid content (the total amount of the preparation components after removing the solvent component) concentration is preferably in the range of 10 to 80 mass %. If the content of the solvent component is within the above-mentioned preferred range, the viscosity can be easily adjusted.

When a polymerization initiator is used, the polymerization initiator can be prepared by a known method just before using the adhesive composition. The polymerization initiator or polymerization inhibitor can be prepared in the form of a solution in which the component (S2) is dissolved in advance. The usage amount of the component (S2) may be appropriately adjusted depending on the type of polymerization initiator or polymerization inhibitor. For example, it is preferably 1 to 50 parts by mass based on 100 parts by mass of the component (S1), and more preferably 5～30 parts by mass. If the usage amount of component (S2) is within the above-mentioned preferred range, the polymerization initiator or polymerization inhibitor can be fully dissolved.

According to the adhesive composition of this embodiment, when temporarily bonding a semiconductor substrate, etc., and a support, an adhesive composition layer is formed between the said semiconductor substrate, etc., and a support, and is hardened. This can form an adhesive layer that temporarily adheres the semiconductor substrate and the like to the support. This adhesive layer is hardened by a cross-linked structure, so it has high heat resistance, and its elastic modulus does not decrease even at high temperatures (for example, 200° C. or higher). Therefore, even when high-temperature processing is performed during the processing of semiconductor substrates or electronic devices, defects such as positional deviation and sinking are less likely to occur. On the other hand, when the above-mentioned adhesive layer is irradiated with light such as laser light, the structure X in the adhesive layer absorbs the light, and the adhesive layer is modified. Therefore, the adhesive force of the adhesive layer is reduced, and the semiconductor substrate and the like can be separated from the support. Therefore, no separation layer is required. Furthermore, since the structure X is introduced into the component (P1), the content ratio of the structure X can be increased without causing problems with solubility. Thus, good separability can be obtained. Furthermore, since the above-mentioned adhesive layer contains polyurethane resin, the urethane bond can be decomposed by acid or alkali, thereby decomposing the adhesive layer. Therefore, even if the residue of the adhesive layer adheres to the semiconductor substrate or the like after being separated from the support, the residue of the adhesive layer can be easily removed by washing with acid or alkali.

(Laminated body) The laminated body of the second aspect of the present invention is characterized in that it is a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, and the adhesive layer is the adhesive of the first aspect. The hardened product of the composition.

FIG. 1 shows an embodiment of the second form of the laminated body. The laminated body 100 shown in FIG. 1 includes a support 1 that can transmit light, an adhesive layer 3, and a semiconductor substrate 4. In the laminated body 100, the support 1, the adhesive layer 3, and the semiconductor substrate 4 are laminated|stacked in this order.

FIG. 2 shows another embodiment of the laminated body of the second form. The laminated body 200 shown in FIG. 2 has the same structure as the laminated body 100 except that the electronic device 456 including the semiconductor substrate 4, the sealing material layer 5 and the wiring layer 6 is laminated on the adhesive layer 3.

FIG. 3 shows another embodiment of the second form of the laminated body. The laminated body 300 shown in FIG. 3 has the same structure as the laminated body 100 except that the electronic device includes the wiring layer 6 .

FIG. 4 shows another embodiment of the second form of the laminated body. The laminated body 400 shown in FIG. 4 has the same structure as the laminated body 100 except that the electronic device 645 including the wiring layer 6, the semiconductor substrate 4 and the sealing material layer 5 is laminated on the adhesive layer 3.

＜Support＞ The support is a member that supports a semiconductor substrate or an electronic device. The support has the property of allowing light to pass through. The support is bonded to the semiconductor substrate or the electronic device via the adhesive layer. Therefore, the support preferably has the strength required to prevent damage or deformation of the semiconductor substrate during thinning of the device, transportation of the semiconductor substrate, mounting on the semiconductor substrate, etc. As a material of the support, for example, glass, silicon, acrylic resin, etc. can be used. Examples of the shape of the support include rectangle, circle, etc., but are not limited thereto. As a support, in order to further achieve high-density integration and improve production efficiency, it is also possible to use an enlarged circular support or a large panel with a quadrilateral shape when viewed from above.

＜Adhering layer＞ The subsequent layer is provided to temporarily bond the semiconductor substrate or electronic device to the support. The subsequent layer is a cured product of the adhesive composition of the above-mentioned first embodiment. The adhesive composition of the first embodiment can be hardened by heating the adhesive composition. The thickness of the subsequent layer is, for example, preferably in the range of 1 μm or more and 200 μm or less, more preferably in the range of 5 μm or more and 150 μm or less.

As described above, the adhesive layer is a cured product of the adhesive composition, and the material (cured product) constituting the adhesive layer preferably satisfies the following characteristics. That is, when the complex elastic modulus of the hardened material is measured under the following conditions, the complex elastic modulus at 200°C is preferably 1.0×10 ⁴ Pa or more, more preferably 5.0×10 ⁴ Pa or more, and still more preferably 1.0. ×10 ⁵ Pa or more. Furthermore, the complex elastic modulus at 200°C is more preferably 1.0×10 ⁶ Pa or more, still more preferably 5.0×10 ⁶ Pa or more, and particularly preferably 1.0×10 ⁷ Pa or more. The upper limit of the complex elastic modulus at 200°C is, for example, 1.0×10 ¹⁰ Pa or less. Moreover, when the complex elastic modulus of the hardened material is measured under the following conditions, the complex elastic modulus at 250°C is preferably 5.0×10 ⁶ Pa or more, more preferably 1.0×10 ⁷ Pa or more. The upper limit of the complex elastic modulus at 250°C is, for example, 1.0×10 ¹⁰ Pa or less.

The complex elastic modulus of the hardened material can be measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition can be coated on a PET film with a release agent, heated at 180°C for 1 hour in an oven under a nitrogen atmosphere to form a test piece with a thickness of 50 μm, and then, The test piece peeled from the PET film (size 5 mm × 40 mm, thickness 50 μm) was measured using the above measuring device. The following conditions can be used for measurement: under tensile conditions with a frequency of 1 Hz, the temperature is raised from the starting temperature of 50°C to 300°C at a heating rate of 5°C/min.

＜Semiconductor substrate or electronic device＞ The semiconductor substrate or the electronic device is temporarily adhered to the support via the adhesive layer.

≪Semiconductor substrate≫ The semiconductor substrate is not particularly limited, and the same semiconductor substrate as exemplified in the above "(adhesive composition)" can be exemplified. The semiconductor substrate can be a semiconductor element or other element, and can have a single-layer or multiple-layer structure.

≪Electronic Devices≫ The electronic device is not particularly limited, and the same electronic devices as those exemplified in the above-mentioned “(adhesive composition)” can be exemplified. The electronic device is preferably a composite including a metal or semiconductor component and a resin that seals or insulates the component. Specifically, the electronic device includes at least one of a sealing material layer and a wiring layer, and may further include a semiconductor substrate. In the laminated body 200 shown in FIG. 2 , the electronic device 456 includes the semiconductor substrate 4 , the sealing material layer 5 , and the wiring layer 6 . In the laminate 300 shown in FIG. 3 , the electronic device 6 includes the wiring layer 6 . In the laminated body 400 shown in FIG. 4 , the electronic device 645 includes the wiring layer 6 , the semiconductor substrate 4 and the sealing material layer 5 .

[Sealing material layer] The sealing material layer is provided to seal the semiconductor substrate and is formed using a sealing material. As the sealing material, a member capable of insulating or sealing a member containing metal or semiconductor may be used. As the sealing material, for example, a resin composition can be used. The sealing material layer 5 is preferably provided so as to cover all the semiconductor substrates 4 on the adhesive layer 3 rather than being provided on each of the semiconductor substrates 4 . The resin used in the sealing material is not particularly limited as long as it can seal and/or insulate metal or semiconductors. Examples thereof include epoxy resin and polysilicone resin. In addition to resin, the sealing material may also contain other components such as fillers. Examples of the filler include spherical silica particles and the like.

≪Wiring Layer≫ The wiring layer can also be called RDL (Redistribution Layer). It is a thin film wiring body that forms the wiring connected to the substrate. It can have a single-layer or multiple-layer structure. The wiring layer may be made of conductors (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and silver) between dielectrics (silicon oxide (SiO _x ), photosensitive resins such as photosensitive epoxides, etc.) - alloy such as tin alloy), but is not limited to this.

Furthermore, in the laminated body shown in FIGS. 1 to 4 , the support 1 and the adhesive layer 3 are adjacent to each other. However, the present invention is not limited to this, and other layers may be formed between the support 1 and the adhesive layer 3 . In this case, the other layers may be made of materials that can transmit light. This makes it possible to appropriately add a layer that imparts better properties to the laminated bodies 100 to 400 without hindering the incidence of light to the adhesive layer 3 . The wavelength of light that can be used varies depending on the type of material constituting the adhesive layer 3 . Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from the following materials that can transmit light of wavelengths that can modify the material constituting the adhesive layer 3 .

(Manufacturing method of laminated body (1)) A method for manufacturing a laminated body according to a third aspect of the present invention is characterized in that it is a method for manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are sequentially laminated. The manufacturing method includes the following steps: The step of applying the adhesive composition of the first form to the above-mentioned support or the semiconductor substrate to form an adhesive composition layer (hereinafter also referred to as the "adhesive composition layer forming step"); passing the above-mentioned semiconductor substrate through the above-mentioned adhesive The step of placing the adhesive composition layer on the above-mentioned support (hereinafter also referred to as the "semiconductor substrate mounting step"); and the step of hardening the above-mentioned adhesive composition layer through the polymerization reaction of the above-mentioned polyurethane resin to form the above-mentioned adhesive composition layer. The step of forming the adhesive layer (hereinafter also referred to as the "adhesive layer forming step").

5 to 6 are schematic step diagrams illustrating one embodiment of the method for manufacturing a laminated body according to this embodiment. 5 (a) to (b) are diagrams illustrating the manufacturing steps of the laminated body 100' in which the support 1, the adhesive composition layer 3', and the semiconductor substrate 4 are sequentially laminated. FIG. 5(a) is a diagram illustrating the steps of forming an adhesive composition layer. FIG. 5(b) is a diagram illustrating a semiconductor substrate mounting step. FIG. 6 is a diagram explaining the steps of forming an adhesive layer. The adhesive composition layer 3' in the laminated body 100' is thermally hardened to form the adhesive layer 3, and the laminated body 100 is obtained.

[Adhesive composition layer formation step] The manufacturing method of the laminated body of this embodiment includes the step of forming an adhesive composition layer. The adhesive composition layer forming step is a step in which the adhesive composition is coated on a support or a semiconductor substrate to form an adhesive composition layer. In FIG. 5(a) , the adhesive composition layer 3' is formed on the support 1 using the adhesive composition.

The method of forming the adhesive composition layer 3' on the support 1 is not particularly limited. For example, methods such as spin coating, dipping, roller knife coating, spray coating, and slit coating can be used. The adhesive composition layer can also be formed on the semiconductor substrate 4 by the same method.

After the adhesive composition layer is formed, baking treatment can be performed. The baking temperature condition is set to a temperature lower than the heating temperature in the adhesive layer forming step described later. The baking conditions may vary depending on the type of curable component contained in the adhesive composition. For example, baking conditions may be performed at a temperature of 70 to 100° C. for 1 to 10 minutes.

[Semiconductor substrate mounting step] The manufacturing method of the laminated body of this embodiment includes the step of placing a semiconductor substrate. The semiconductor substrate mounting step is a step of mounting the semiconductor substrate on the support via the adhesive composition layer. Thereby, the laminated body 100' can be obtained. In FIG. 5( b ), the semiconductor substrate 4 is placed on the support 1 via the adhesive composition layer 3 ′ formed on the support 1 .

The method of placing the semiconductor substrate 4 on the support 1 via the adhesive composition layer 3' is not particularly limited, and a method commonly used as a method of arranging the semiconductor substrate at a predetermined position can be used.

[Subsequent layer formation step] The manufacturing method of the laminated body of this embodiment includes the step of forming an adhesive layer. The subsequent layer forming step is a step in which the adhesive composition layer is cured by polymerization reaction of the polyurethane resin ((P1) component) in the adhesive composition layer to form the adhesive layer. Thereby, the laminated body 100 can be obtained. In FIG. 6 , the adhesive layer 3 is formed by hardening the adhesive composition layer 3 ′.

The polymerization reaction of the component (P1) in the adhesive composition layer can be performed by selecting an appropriate method according to the type of polymerizable carbon-carbon double bonds contained in the component (P1). For example, when the component (P1) contains a methacryloyl group or an acrylyl group, the polymerization reaction of the component (P1) can be performed by heating.

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 a time sufficient to polymerize and harden the component (P1). The heating time is, for example, preferably 5 to 180 minutes, more preferably 10 to 120 minutes, or even more preferably 15 to 60 minutes. The above-mentioned hardening reaction can be carried out in a nitrogen atmosphere, for example.

Through this step, the component (P1) in the adhesive composition layer 3' is cross-linked and hardened, and the adhesive layer 3 is formed as a hardened product of the adhesive composition layer 3'. Thereby, the support 12 and the semiconductor substrate 4 are temporarily connected. As a result, the laminated body 100 can be obtained.

[any step] The manufacturing method of the laminated body of this embodiment may also include other steps in addition to the above-mentioned steps. Examples of other steps include various mechanical or chemical treatments (polishing, chemical mechanical polishing (CMP) and other thin film treatments), chemical vapor deposition (CVD), physical vapor deposition (PVD) and other high-temperature and vacuum treatments. Treatment, treatment using chemicals such as organic solvents, acidic treatment solutions, alkaline treatment solutions, electroplating treatment, irradiation of active light, heating, cooling treatment, etc.).

(Manufacturing method of laminated body (2)) A method for manufacturing a laminated body according to a fourth aspect of the present invention is characterized in that, after obtaining the laminated body using the method for manufacturing a laminated body according to the third aspect, the invention further includes an electronic device forming step of forming an electronic device, and the electronic device is made of metal. Or a composite of a semiconductor component and a resin that seals or insulates the component.

The laminate system obtained by the method for manufacturing a laminate of this embodiment is a laminate in which a support, an adhesive layer, and an electronic device are sequentially laminated. This laminated body can be obtained by subjecting the laminated body obtained by the manufacturing method of the laminated body of the said 3rd aspect to the electronic device formation process.

[Electronic device forming step] The method of manufacturing a laminated body according to this embodiment includes an electronic device forming step. The electronic device forming step is a step of forming an electronic device that is a composite of a member including a metal or a semiconductor and a resin that seals or insulates the member. The electronic device forming step may include any one of a sealing step, a grinding step, and a wiring layer forming step. In one embodiment, the electronic device forming step includes a substrate fixing step and a sealing step. In this case, the electronic device forming step may further include a grinding step and a wiring layer forming step.

・About sealing procedures The sealing step is a step of sealing the substrate fixed on the support using a sealing material. In FIG. 7( a ), a laminated body 110 is obtained in which the entire semiconductor substrate 4 temporarily adhered to the support 1 via the adhesive layer 3 is sealed by the sealing material layer 5 .

In the sealing step, the sealing material heated to, for example, 130 to 170° C. is maintained in a high-viscosity state, is supplied to the adhesive layer 3 to cover the semiconductor substrate 4, and is compressed and molded, thereby creating a sealing material on the adhesive layer 3. Laminated body 110 of material layer 5 . At this time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500 N/cm ² .

The sealing material layer 5 is preferably provided so as to cover all the semiconductor substrates 4 on the adhesive layer 3 rather than being provided on each of the semiconductor substrates 4 .

・About grinding procedures The grinding step is a step of grinding the sealing material portion (sealing material layer 5) in the sealing body in such a manner that a portion of the semiconductor substrate is exposed after the above-mentioned sealing step. The sealing material portion is ground by, for example, the following method: as shown in FIG. 7(b) , the sealing material layer 5 is ground to a thickness substantially equal to that of the semiconductor substrate 4 .

・About wiring layer formation steps The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor substrate after the grinding step. In FIG. 7(c), the wiring layer 6 is formed on the semiconductor substrate 4 and the sealing material layer 5. Thereby, the laminated body 120 can be obtained. In the laminated body 120 , the semiconductor substrate 4 , the sealing material layer 5 and the wiring layer 6 constitute an electronic device 456 .

As a method of forming the wiring layer 6, for example, the following method can be cited. First, a dielectric layer of silicon oxide (SiO _x ), photosensitive resin, etc. is formed on the sealing material layer 5 . The dielectric layer containing silicon oxide can be formed by, for example, sputtering, vacuum evaporation, or the like. The dielectric layer containing the photosensitive resin can be formed by coating the photosensitive resin on the sealing material layer 5 using methods such as spin coating, dipping, roller knife coating, spray coating, and slit coating.

Then, conductors such as metal are used to form wiring on the dielectric layer. As a method of forming the wiring, for example, known semiconductor manufacturing methods such as photolithography (resist lithography) and etching can be used. Examples of such photolithography include photolithography using a positive resist material and photolithography using a negative resist material.

In the method of manufacturing a laminated body of this embodiment, bumps can be formed or components can be mounted on the wiring layer 6 . The components can be mounted on the wiring layer 6 using, for example, a placement machine.

(Manufacturing method of laminated body (3)) A method for manufacturing a laminated body according to a fifth aspect of the present invention is characterized in that it is a method for manufacturing a laminated body in which a support, an adhesive layer, and an electronic device are sequentially laminated, and the manufacturing method includes the following steps: The step of applying the adhesive composition of the above-mentioned first form to form a layer of the above-mentioned adhesive composition (the adhesive composition layer forming step); the electronic device forming step of forming an electronic device on the above-mentioned adhesive composition layer, the above-mentioned The electronic device is a composite including a metal or semiconductor member and a resin that seals or insulates the member (electronic device forming step); and a step of hardening the adhesive composition layer to form an adhesive layer (adhesive layer forming step) .

The laminated body obtained by the manufacturing method of the laminated body of this embodiment is a laminated body in which a support body, an adhesive layer, and an electronic device are laminated|stacked in this order similarly to the manufacturing method concerning the said 4th aspect.

In the manufacturing method of this embodiment, the adhesive composition layer forming step can be performed in the same manner as the adhesive composition layer forming step in the manufacturing method of the laminated body of the third aspect.

In the manufacturing method of this embodiment, after the adhesive composition layer forming step, the electronic device forming step is performed. As the electronic device forming step, a wiring layer forming step may be included. The electronic device forming step may further include a semiconductor substrate mounting step, a sealing step, a grinding step, and the like. Moreover, the electronic device forming step may be a step of placing a sealing body (which seals the semiconductor substrate with a sealing material) on the support through the adhesive composition layer.

The step of forming the subsequent layer can be performed in the same manner as the step of forming the subsequent layer in the method of manufacturing the laminated body of the third aspect.

After the subsequent layer forming step, an electronic device forming step may be further performed if necessary. The electronic device forming step may include, for example, a semiconductor substrate mounting step, a sealing step, and a grinding step.

According to the manufacturing method of the laminated body of the above-mentioned third to fifth aspects, the support and the semiconductor substrate or the electronic device are temporarily connected via the highly heat-resistant adhesive layer. Therefore, it is possible to stably manufacture the support and the adhesive layer laminated in this order. , and laminates of semiconductor substrates or electronic devices. The laminate system is a laminate produced in a process based on fan-out technology in which terminals provided on a semiconductor substrate are mounted on wiring layers extending outside the chip area.

(Manufacturing method of electronic components) A method for manufacturing an electronic component according to a sixth aspect of the present invention is characterized in that, after obtaining the laminated body using the method for manufacturing a laminated body in any one of the above-described third to fifth aspects, the method includes the following steps: The step of irradiating the above-mentioned adhesive layer with light to modify the above-mentioned adhesive layer, thereby separating the above-mentioned electronic device from the above-mentioned support (hereinafter also referred to as the "separation step"); and using acid or alkali to separate the above-mentioned adhesive layer. The step of removing the above-mentioned adhesive layer by decomposing the urethane bond (hereinafter also referred to as the "adhesive layer removal step").

8 is a schematic step diagram illustrating one embodiment of a manufacturing method of a semiconductor package (electronic component). FIG. 8(a) is a diagram showing the laminated body 120, FIG. 8(b) is a diagram explaining the separation step, and FIG. 8(c) is a diagram explaining the adhesive layer removal step.

[Separation step] The separation step is a step in which the electronic device 456 is separated from the support 1 by irradiating light (arrow) to the adhesive layer 3 through the support 1 to modify the adhesive layer 3 . As shown in FIG. 8(a) , in the separation step, the adhesive layer 3 is irradiated with light (arrow) through the support 1 that can transmit light, thereby modifying the adhesive layer 3 .

The wavelength of the light used in the separation step is selected based on the wavelength of light that can be absorbed by the structure X contained in the adhesive layer 3 in the wavelength range of 300 to 800 nm. The type of light to be irradiated can be appropriately selected according to the transmittance of the support 1. For example, solid lasers such as YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, and fiber laser can be used. Liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, free electron lasers and other laser light, non-laser light. Thereby, the adhesive layer 3 is modified, and the support 1 and the electronic device 456 can be easily separated.

When irradiating laser light, the following conditions can be cited as an example of laser light irradiation conditions. The average output value of laser light is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of laser light is preferably between 20 kHz and below 60 kHz, and more preferably between 30 kHz and below 50 kHz. The scanning speed of laser light is preferably above 100 mm/s and below 10000 mm/s.

After the adhesive layer 3 is irradiated with light (arrow) and modified, the support 1 is separated from the electronic device 456 as shown in FIG. 8(b) . For example, the support 1 and the electronic device 456 are separated by applying force along the direction in which the support 1 and the electronic device 456 are separated from each other. Specifically, while one of the support 1 or the electronic device 456 side (wiring layer 6) is fixed to the platform, the other is suction-held and lifted using a separation plate equipped with an adsorption pad such as a bellows pad. , thereby enabling the support 1 to be separated from the electronic device 456 . The force applied to the laminated body 200 can be appropriately adjusted according to the size of the laminated body 200, etc., and is not limited. For example, if the diameter of the laminated body is about 300 mm, the force exerted on the laminated body 200 can be adjusted by applying 0.1 to 5 kgf (0.98 to 49 N). ) to properly separate the support 1 and the electronic device 456.

[Next layer removal step] The manufacturing method of electronic components of this embodiment includes an adhesive layer removal step. The subsequent layer removal step is a step of using acid or alkali to decompose the urethane bonds in the adhesive layer to remove the above-mentioned adhesive layer. In FIG. 8(b) , after the separation step, the adhesive layer 3 is attached to the electronic device 456 . In this step, the adhesive layer 3 is decomposed using acid or alkali, thereby removing the adhesive layer 3 to obtain the electronic component 50 .

In this step, acid or alkali is used to decompose the urethane bond in the adhesive layer 3. The subsequent layer 3 contains a polyurethane resin formed by copolymerization of the above-mentioned component (I) and (O), or a cross-linked polyurethane resin formed by polymerization of the above-mentioned component (P1). These polyurethane resins can be decomposed by cutting the urethane bonds by treating them with acid or alkali. Thereby, the adhesive layer 3 can be decomposed, and the residue attached to the adhesive layer 3 of the electronic device 456 can be removed.

The acid or alkali used in this step is not particularly limited as long as it can decompose the urethane bond. Examples of the acid capable of decomposing a urethane bond include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, and the like. Examples of the base capable of decomposing the urethane bond include, but are not limited to, inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine. .

The above acid or alkali can be dissolved in a solvent and used as a treatment liquid for removing the adhesive layer. As the above-mentioned solvent, a polar solvent is preferred, and examples thereof include dimethylstyrene (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, and ethylene glycol. alcohol, propylene glycol, etc. The above-mentioned treatment liquid for removing the adhesive layer may also contain known additives such as surfactants in addition to the above-mentioned components. The acid or alkali content in the treatment liquid is not particularly limited, but may be, for example, 1 to 50% by mass. Moreover, as content of the polar solvent in the said processing liquid, 50-99 mass % can be mentioned. As a treatment solution for removing the adhesive layer, a commercially available alkaline treatment solution or acidic treatment solution can be used. Examples of commercially available treatment liquids include ST-120 and ST-121 (both manufactured by Tokyo Oika Kogyo Co., Ltd.). By bringing the above-described treatment liquid containing acid or alkali into contact with the adhesive layer 3, the urethane bonds in the adhesive layer 3 are decomposed, and the adhesive layer 3 can be removed.

In the method of manufacturing an electronic component in this embodiment, after the above-mentioned step of removing the adhesive layer, the electronic component 50 may further be subjected to processes such as solder ball formation, cutting, or oxide film formation.

According to the manufacturing method of electronic components of this embodiment, an adhesive composition containing a polyurethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond and a polymerization initiator (A) is used, and the adhesive composition is hardened. , thereby temporarily bonding the semiconductor substrate and the like to the support. Therefore, it is possible to form a highly heat-resistant adhesive layer that can withstand high-temperature processing in electronic device formation processes and the like. The polyurethane resin (P1) has a structural unit (u1) including a structure (structure , the bonding force decreases. Therefore, even if there is no separation layer, the semiconductor substrate etc. which are temporarily connected can be easily separated from the support. Structure X is introduced in the form of a structural unit of the polyurethane resin (P1). Therefore, the content of structure X can be increased while maintaining good adhesion. As a result, good adhesion and detachability can be achieved at the same time. Furthermore, residues attached to the adhesive layer on the semiconductor substrate or the like separated from the support can be easily removed by decomposing the urethane bonds in the adhesive layer using acid or alkali. [Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

<Synthesis Example 1 of Polyurethane Resin: Polyurethane Resin (P1-1)> Add 16 parts of propylene glycol monomethyl ether acetate (PGMEA), polycarbonate diol (long chain), and 16 parts of polycarbonate diol (short chain) to a flask equipped with a stirrer, dropping funnel, condenser tube and thermometer. , 13 parts of glycerol monoacrylate, 20 parts of monomer (T-33), and inhibitors were uniformly mixed under nitrogen flow. Next, 35 parts of isophorone diisocyanate was put into a dropping funnel and added dropwise at a constant rate for 30 minutes. After the dropwise addition, aging was performed for 30 minutes. Thereafter, a bismuth catalyst is added, the temperature is raised to 65°C, and aging is performed for 4 to 5 hours. Next, 2HEA (2-hydroxyethyl acrylate) was added, aging was performed for 1 hour, and the reaction was completed when the isocyanate group (NCO) disappeared. The weight average molecular weight (Mw) of the obtained polyurethane resin (P1-1) was 15,800. The C=C equivalent (the molecular weight of the polyurethane resin calculated per 1 equivalent of polymerizable carbon-carbon double bonds) of the polyurethane resin (P1-1) is 1230 g/eq.

<Synthesis Example 2 of Polyurethane Resin: Polyurethane Resin (P1-2)> Polyurethane resin (P1-2) was synthesized in the same manner as in Synthesis Example 1 except that the monomer composition was set to the composition shown in Table 1. The weight average molecular weight (Mw) of the obtained polyurethane resin (P1-2) was 32,000. The C=C equivalent (the molecular weight of the polyurethane resin calculated per 1 equivalent of polymerizable carbon-carbon double bonds) of the polyurethane resin (P1-2) is 1230 g/eq.

<Synthesis Example 3 of Polyurethane Resin: Polyurethane Resin (P1-3)> Polyurethane resin (P1-3) was synthesized in the same manner as in Synthesis Example 1 except that the monomer composition was as shown in Table 1. The weight average molecular weight (Mw) of the obtained polyurethane resin (P1-3) was 33,200. The C=C equivalent of the polyurethane resin (P1-3) (the molecular weight of the polyurethane resin calculated per 1 equivalent of polymerizable carbon-carbon double bonds) is 1230 g/eq.

<Synthesis Example 4 of Polyurethane Resin: Polyurethane Resin (P2-1)> Polyurethane resin (P2-1) was synthesized in the same manner as in Synthesis Example 1 except that the monomer composition was as shown in Table 1. The weight average molecular weight (Mw) of the obtained polyurethane resin (P2-1) was 16,000. The C=C equivalent (the molecular weight of the polyurethane resin calculated per 1 equivalent of polymerizable carbon-carbon double bonds) of the polyurethane resin (P2-1) is 1230 g/eq.

[Table 1] Synthesis example 1 Synthesis example 2 Synthesis example 3 Synthesis example 4 Isophorone diisocyanate 35 36 29 35 Polycarbonate diol (long chain) 16 10.5 5 26 Polycarbonate diol (short chain) 16 10.5 5 26 Glyceryl monoacrylate 13 13 13 13 Single unit (U1-1) 20 30 - - Single unit (U1-2) - - 48 - (mass%)

Details of each ingredient in Table 1 are as follows. Isophorone diisocyanate (IPDI).

[Chemical 12]

Polycarbonate diol (long chain): Polycarbonate diol (R=-(CH ₂ ) ₆ -, -(CH ₂ ) ₅ -) represented by the following formula (PC-1-1), Mw= 1,000. Polycarbonate diol (short chain): polycarbonate diol (R=-(CH ₂ ) ₆ -, -(CH ₂ ) ₅ -) represented by the following formula (PC-1-1), Mw= 500.

[Chemical 13]

Glyceryl monoacrylate (GLMA).

[Chemical 14]

Monomer (U1-1): a compound represented by the following formula (U1-1). Monomer (U1-2): a compound represented by the following formula (U1-2).

[Chemical 15]

<Preparation of adhesive composition> (Examples 1 to 3, Comparative Example 1) The ingredients shown in Table 2 were mixed to prepare adhesive compositions for each example.

[Table 2] (P1)Ingredients (A)Ingredients (S)Ingredients Example 1 (P1)-1 [100] (A)-1 [0.5] (S)-1 [185] Example 2 (P1)-2 [100] (A)-1 [0.5] (S)-1 [185] Example 3 (P1)-3 [100] (A)-1 [0.5] (S)-1 [185] Comparative example 1 (P2)-1 [100] (A)-1 [0.5] (S)-1 [185]

In Table 2, each abbreviation has the following meaning. The value in [ ] is the blending amount (parts by mass). (P1)-1 to (P1)-3: the polyurethane resins (P1-1) to (P1-3) synthesized in the above synthesis examples 1 to 3. (P2)-1: The polyurethane resin (P2-1) synthesized in the above-mentioned Synthesis Example 4. (A)-1: Peroxide (Percumyl (registered trademark) D, Nippon Oils and Fats Co., Ltd.). (S)-1: PGMEA.

＜Manufacture of laminated body＞ The adhesive compositions of each example were spin-coated on a bare silicon wafer (5 mm × 5 mm), and baked at 100°C for 10 minutes to form an adhesive layer with a film thickness of 25 μm. Next, use a die bonder (manufactured by TRESKY) to heat the flat plate of the die bonder to 50°C, and press the above-mentioned bare chip through the above-mentioned adhesive layer under the conditions of 350g pressure and 90 seconds. to bare glass support (thickness 0.7 mm, E-XG, CORNING Company). Next, heating was performed at 180° C. for 15 minutes to harden the adhesive layer, thereby obtaining a laminated body.

[Evaluation of separation] Using IPEX848 (308 nm XeCl, Light Machinery), under the conditions of scanning speed of 15.6 mm/sec (overlap 80%), frequency of 60 kHz, and beam size of 2×14 mm, Laser light with a wavelength of 308 nm is irradiated from the side of the bare glass support of the above-mentioned laminate to the above-mentioned adhesive layer. Afterwards, an attempt was made to peel off the bare glass. Separability was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3. Evaluation criteria 〇: Peeling occurred when the laser light irradiation dose was 300 mJ/cm ² or less. ×: No peeling occurred when the laser irradiation dose was 300 mJ/cm ² or less.

[table 3] Separation Example 1 〇 Example 2 〇 Example 3 〇 Comparative example 1 ×

From the results shown in Table 3, it was confirmed that the adhesive layer formed using the adhesive compositions of Examples 1 to 3 also functions as a separation layer.

1:Support 3:Add layer 3': Adhesive composition layer 4: Semiconductor substrate 5:Sealing material layer 6: Wiring layer 20: Laminated body 50:Electronic parts 100:Laminated body 100':Laminated body 110:Laminated body 120:Laminated body 200:Laminated body 300:Laminated body 400:Laminated body 456:Electronic devices 645:Electronic devices

FIG. 1 is a schematic diagram showing an embodiment of a laminated body to which the present invention is applied. FIG. 2 is a schematic diagram showing an embodiment of a laminated body to which the present invention is applied. FIG. 3 is a schematic diagram showing an embodiment of a laminated body to which the present invention is applied. FIG. 4 is a schematic diagram showing an embodiment of a laminated body to which the present invention is applied. FIG. 5 is a schematic step diagram illustrating one embodiment of a manufacturing method of a laminated body 100' in which a support, an adhesive composition layer, and a semiconductor substrate are sequentially laminated. FIG. 5(a) is a diagram illustrating the adhesive composition layer forming step, and FIG. 5(b) is a diagram illustrating the semiconductor substrate mounting step. FIG. 6 is a diagram explaining the steps of forming an adhesive layer. FIG. 7 is a schematic step diagram illustrating one embodiment of the method of manufacturing the laminated body 120. FIG. 7(a) is a diagram explaining the sealing step, FIG. 7(b) is a diagram explaining the grinding step, and FIG. 7(c) is a diagram explaining the wiring layer forming step. FIG. 8 is a schematic step diagram illustrating one embodiment of a method of manufacturing a semiconductor package (electronic component) from the laminated body 120. FIG. 8(a) is a diagram showing the laminated body 200, FIG. 8(b) is a diagram explaining the separation step, and FIG. 8(c) is a diagram explaining the adhesive layer removal step.

Claims (8)

An adhesive composition for forming an adhesive layer that temporarily connects a semiconductor substrate or electronic device and a support that can transmit light, the adhesive composition containing: Polyurethane resin (P1) containing polymerizable carbon-carbon unsaturated bonds, and Polymerization initiator (A), The above-mentioned polyurethane resin (P1) has a structural unit (u1) including a structure capable of absorbing at least part of light in the range of 300 to 800 nm wavelength. The adhesive composition of claim 1, wherein the above structural unit (u1) is a structural unit derived from a compound represented by the following general formula (u1-1) or (u1-2), [Chemical 1] [In the formula (u1-1), X ¹ is an n1 valent group containing a structure capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm; Y ¹ is a divalent linking group, and n1 is an integer from 2 to 4; A plurality of Y ¹ may be the same or different from each other; in the formula (u1-2), X ² is a valent base containing a structure capable of absorbing at least part of the light in the wavelength range of 300 to 800 nm; Y ² is each independently A 3-valent linking base, Y ³ is an n2-valent linking base; n2 is an integer from 2 to 4; a plurality of X ² can be the same or different from each other; a plurality of Y ² can be the same or different from each other]. The adhesive composition of claim ² , wherein The base of acylbenzene skeleton or benzotriazole skeleton. The adhesive composition according to any one of claims 1 to 3, wherein a composite system of a member including a metal or a semiconductor as the electronic device and a resin for sealing or insulating the member is laminated on the support via the adhesive layer. body. A laminated body in which a support capable of transmitting light, an adhesive layer, and a semiconductor substrate or electronic device are laminated in this order. The above-mentioned adhesive layer is a hardened product of the adhesive composition according to any one of claims 1 to 4. A method for manufacturing a laminated body, which is a method for manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are sequentially laminated. The manufacturing method includes the following steps: The step of coating the adhesive composition according to any one of claims 1 to 4 on the above-mentioned support or semiconductor substrate to form an adhesive composition layer; The step of placing the semiconductor substrate on the support via the adhesive composition layer; and The step of hardening the adhesive composition layer to form the adhesive layer. A method for manufacturing a laminated body, which is a method for manufacturing a laminated body in which a support capable of transmitting light, an adhesive layer, and an electronic device are sequentially laminated, After the laminated body is obtained by the method of manufacturing a laminated body according to Claim 6, the method further includes the step of forming an electronic device, which is a composite body including a metal or semiconductor component and a resin that seals or insulates the component. A manufacturing method of electronic components, which includes the following steps after obtaining the laminated body through the manufacturing method of the laminated body according to claim 7: The step of irradiating light to the adhesive layer through the support to modify the adhesive layer, thereby separating the electronic device from the support; and A step of removing the adhesive layer attached to the electronic device by decomposing the urethane bonds in the adhesive layer using acid or alkali.