TW202332711A - Adhesive composition, laminate, manufacturing method of laminate, and manufacturing method of electronic components wherein the adhesive composition is used to form a temporary adhesive layer between a semiconductor substrate or electronic device and a light transparent support - Google Patents

Abstract

The subject of the present invention is to provide an adhesive composition that does not require a separation layer, a laminate manufactured using the adhesive composition, a method for manufacturing the laminate, and a method for manufacturing electronic components using the adhesive composition. The present invention relates to an adhesive composition used to form a temporary adhesive layer between a semiconductor substrate or electronic device and a light transparent support. The above-mentioned adhesive composition contains a resin (P1) and a polymerization initiator (A). The resin (P1) has a structural unit (u1) including a structure that absorbs at least a part of light in the wavelength range of 300-800 nm, and the storage modulus (G') of the adhesive layer formed by the adhesive composition at 150 DEG C is 1.5×10<SP>5</SP> Pa or less.

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) containing 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, there are known fan-in WLP (Fan-in Wafer Level Package) in which terminals located at the end of a bare chip are rearranged in the chip area. As a semiconductor package based on fan-out technology, there are known fan-out WLP (Fan-out Wafer Level Package) in which the terminals are rearranged outside the chip area.

In recent years, in particular, fan-out technology has been applied to fan-out PLP (Fan-out Panel Level Package), which arranges semiconductor elements on a panel and packages them, as a way to realize semiconductor packaging. Methods such as further high integration, thinning, and miniaturization are attracting attention.

In order to achieve miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in which the components are incorporated. However, if the thickness of the substrate is reduced, its strength will be reduced, and the substrate will be easily damaged when manufacturing a semiconductor package. In view of this, 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 from the viewpoint that 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]

Previous adhesives usually require a separation layer 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 makes the operation complicated.

The present invention was completed in view of the above circumstances, and its object is to provide an adhesive composition that does not require a separation layer, a laminated body produced using the adhesive composition, a method for producing 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 to a light-transmitting support. The adhesive composition contains resin (P1), and a polymerization initiator (A), the above-mentioned resin (P1) has a structural unit (u1) including a structure that absorbs at least part of light in the range of 300 to 800 nm wavelength, and an adhesive composition formed from the above-mentioned adhesive composition The storage modulus (G') of the layer at 150°C is 1.5×10 ⁵ Pa or less.

A second aspect of the present invention 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 composition of the first aspect. The hardened body.

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: Or the step of applying the adhesive composition of the above-mentioned first aspect on a semiconductor substrate to form an adhesive composition layer; the step of placing the above-mentioned semiconductor substrate on the above-mentioned support through the above-mentioned 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 of manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and an electronic device are sequentially laminated, and further has the advantage of obtaining a laminated body by the method of manufacturing a laminated body of the above-mentioned third aspect. Then, there is an electronic device forming step to form an electronic device. The electronic device is a composite of a component made of metal or a semiconductor and a resin that seals or insulates the component.

A fifth aspect of the present invention is a method for manufacturing an electronic component, which has the following steps: after obtaining the laminated body by the manufacturing method of the laminated body of the above-mentioned fourth aspect, irradiating the above-mentioned adhesive layer with light through the above-mentioned support. The step of degrading the adhesive layer to separate the electronic device from the support; and the step of removing the adhesive layer attached to the electronic device. [Effects of the invention]

According to the present invention, it is possible to provide an adhesive composition in which the adhesive layer can be easily removed without requiring a separation layer, a laminated body produced using the adhesive composition, a method for producing the laminated body, and electronic products using the adhesive composition. Methods of manufacturing parts.

In this specification and the patent scope of this application, "aliphatic" is a relative concept to aromatic, and is defined to mean groups, compounds, etc. that do not have aromatic properties. Unless otherwise stated, "alkyl" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same is true for the alkyl group in the alkoxy group. Unless otherwise stated, "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "haloalkyl group" is a group in which a part or all of the hydrogen atoms of an alkyl group are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. "Fluoroalkyl" or "fluoroalkylene" refers to a group in which part or all of the hydrogen atoms of an alkyl or alkylene group are substituted with fluorine atoms. "Structural unit" refers to the monomeric 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 by a monovalent group, and the case where a methylene group (-CH ₂ -) is substituted by a divalent group. These two situations. The concept of "exposure" 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. The concept of "hydroxystyrene derivatives" includes those in which the hydrogen atom at the alpha position of hydroxystyrene is substituted with other substituents such as alkyl, haloalkyl, 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 the hydrogen atom of the hydroxyl group may be substituted with an organic group; the hydrogen atom at the α position may be substituted with a substituent. The benzene ring of hydroxystyrene has substituents other than hydroxyl groups bonded to it. Furthermore, unless otherwise stated, the α-position (α-position carbon atom) refers to the carbon atom bonded to the benzene ring. Examples of the substituent for substituting the α-position hydrogen atom of 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 haloalkyl group as the α-position substituent include a group in which part or all of the hydrogen atoms in the above-mentioned “alkyl group as the α-position substituent” are substituted 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. Specific examples of the hydroxyalkyl group as the α-position substituent include a group in which part or all of the hydrogen atoms in the above-mentioned “alkyl group as the α-position substituent” are substituted with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

In this specification and the patent scope of this application, depending on the structure shown in the chemical formula, asymmetric carbon may exist, and enantiomers and diastereomers may exist. In this case, Use a formula to represent these isomers representatively. These isomers can be used individually or in the form of mixtures.

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

＜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 the electronic device is temporarily adhered to the support and fixed (temporarily adhered) to the support. After the process is completed, Separation from the support.

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

"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 and circuits formed on the surface of the semiconductor substrate. The electronic device is preferably a composite of a member made of metal or a semiconductor and a resin that seals or insulates the member. The electronic device may also 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 the semiconductor substrate or electronic device. As will be described later, the support is composed of a member that has light-transmitting properties and supports the semiconductor substrate.

＜Resin (P1): (P1) component＞ The adhesive composition of this embodiment contains resin (hereinafter, also referred to as "(P1) component"). The component (P1) has a structural unit (u1) including a structure that absorbs at least part of the light in the range of 300 to 800 nm wavelength. Thereby, by irradiating the adhesive layer with light in the wavelength range of 300 to 800 nm, the structural unit (u1) absorbs the light and generates heat. Thereby, the adhesive layer can be modified.

Examples of the structure included in the structural unit (u1) that absorbs at least part of the light in the wavelength range of 300 to 800 nm (hereinafter also referred to as "structure Methyl ketone skeleton, benzoylmethane skeleton, benzoylbenzene skeleton, or benzotriazole skeleton. The aromatic fused ring skeleton contains a fused 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 fused ring may be composed only of an aromatic ring, or may be a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, but is preferably a fused 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. The component (P1) having the structural unit (u1) can be obtained by polymerizing the polymerizable monomer containing the structure X. The component (P1) may also contain structural units other than the structural unit (u1). In this case, the component (P1) can be obtained by polymerizing a polymerizable monomer containing structure X and a polymerizable monomer capable of deriving other structural units.

The component (P1) is a resin in which the storage modulus (G') of the adhesive composition layer formed of the adhesive composition at 150°C is 1.5×10 ⁵ Pa or less. The adhesive composition after hardening has a storage modulus equal to or less than the above-mentioned upper limit, so that the adhesiveness becomes good.

The storage modulus (G') of the adhesive composition at 150°C can be measured as follows. The adhesive composition is coated on the PET film with a release agent, and heated at 50°C and 100°C for 60 minutes each in an atmospheric pressure oven to form an adhesive composition layer with a thickness of 0.5 mm. Next, the storage modulus (G′) at 150°C was measured using a dynamic viscoelasticity measuring device for the adhesive composition layer peeled off from the PET film. As a dynamic viscoelasticity measuring device, for example, Rheogel-E4000 (manufactured by UBM Co., Ltd.) can be used. The measurement conditions are as follows: make the sample shape of the adhesive composition layer 2.5 mm × 2.5 mm × 0.5 mm, and heat it from room temperature to 215°C at a rate of 5°C/min under shear conditions with a frequency of 1 Hz. , thereby measuring the storage modulus (G') at 150°C.

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

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. , especially preferably 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. If 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 too hard and the cleanability will be good. The above-mentioned equivalent number is the molecular weight of component (P1) per 1 equivalent of polymerizable carbon-carbon unsaturated bond.

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

"Polyisocyanate compound: (I) ingredient" 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 generally used for producing urethane resins can be used without particular limitations. Blocked polyisocyanate is a compound in which the isocyanate group of the polyisocyanate is blocked and deactivated by reaction with a blocking agent. The blocked polyisocyanate used as component (I) is preferably one in which isocyanate groups are blocked with a thermally dissociable blocking agent. Examples of thermally dissociable end-capping agents include end-capping agents such as oximes, diketones, phenols, and caprolactams. In a blocked polyisocyanate obtained using a thermally dissociable blocking agent, isocyanate groups are inactive at normal temperature, and the thermally dissociable blocking agent is dissociated by heating to generate isocyanate groups again.

Specific examples of the polyisocyanate include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane diisocyanate, isophor Alicyclic diisocyanates such as ketone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; and toluene diisocyanate , 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, benzidine diisocyanate, terephthalene diisocyanate, naphthalene diisocyanate 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 also 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 Chemicals 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. As for the blocking agent, it suffices 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, and There are no particular limitations, and publicly known ones can be used without particular limitations. Specific examples of the blocking agent include, for example, lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; methyl ethyl ketoxime , methyl isopentyl ketone oxime, methyl isobutyl ketone oxime, formamide oxime, acetamide oxime, acetone oxime, diethyl monooxime, benzophenone oxime, cyclohexanone oxime and other oxime compounds; 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-naphthol, etc. Alcohol compounds such as ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; alkyl malonate, dialkyl malonate, Active methylene compounds such as acetoacetate alkyl ester and acetoacetone; etc. One type of terminal blocking 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, acetate cellosolve, etc.), under heating at about 50 to 100°C, and blocking as needed. Proceed in the presence of 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, known ones can be used, for example, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium phenolate, and potassium methoxide; tetraalkanes such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium. Ammonium hydroxides; organic weak acid salts such as acetate, octanoate, myristate, and benzoate; and alkali metals of alkyl carboxylic acids such as acetic acid, caproic acid, octanoic acid, myristic acid, etc. Salt; 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 component (I), a blocked polyisocyanate in which an isocyanate group is blocked 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 generally used for producing urethane resins can be used without particular limitations. Examples of the (O) component include polyols containing a polymerizable carbon-carbon unsaturated bond (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 (O1) component 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 trihydric or higher molecular weight polyols include trihydric alcohols such as glycerol and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol; and pentahydric alcohols such as xylitol. ; Six-valent alcohols such as sorbitol, mannitol, allitol, idbitol, sweet alcohol, aldrose, inositol, and dipentaerythritol; seven-valent alcohols such as cycitol; and eight-valent alcohols such as sucrose; wait.

Specific examples of the component (O1) include: glycerol mono(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, Diglyceryl 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, meaning 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 -Pentylene glycol, 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 glycol and bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; sorbitol , mannitol, allol, idbitol, sweet alcohol, aldrose, myo-inositol, dipentaerythritol and other six-valent alcohols; heptol and other seven-valent alcohols; and sucrose and other eight-valent alcohols; etc. Among them, the low molecular weight polyol is preferably a glycol (diol).

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

When using a low molecular polyol 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.

[Phenol resin] The phenol resin may be a novolak type phenol resin or a resol 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 phenolic phenol resin can be obtained by 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-xylenol. Phenol, 3,4-xylenol and other xylenols; 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; ortho- Isopropenylphenols such as isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)quin , 9,9-bis(4-hydroxy-3-methylphenyl)benzoate, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane and other polyhydroxyphenols.

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 haloalkyl 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 (n _ax1 +1) valence. 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 haloalkyl 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, iso Propyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The haloalkyl group having 1 to 5 carbon atoms in R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted 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 fluoroalkyl group having 1 to 5 carbon atoms. In view of ease 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 means a non-aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is usually preferably a saturated hydrocarbon group. 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 even more preferably a carbon atom. The number is 1 to 4, and the most preferable number is 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred. Specific examples thereof include: methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -] , propylene [-(CH ₂ ) ₃ -], butylene [-(CH ₂ ) ₄ -], pentyl [-(CH ₂ ) ₅ -], etc. The number of carbon atoms of the branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. . The branched aliphatic hydrocarbon group is preferably a branched alkylene group. 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 propylene; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -alkyl propylene; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ )CH ₂ CH ₂ -, etc. Alkyl alkylene butyl, etc. 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 fluoroalkyl group having 1 to 5 carbon atoms substituted by 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 this structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a substituent containing a heteroatom in the ring structure; A group in which the terminal of a linear or branched aliphatic hydrocarbon group is bonded to the above-mentioned cyclic aliphatic hydrocarbon group, and the above-mentioned cyclic aliphatic hydrocarbon group is interposed between the linear or branched aliphatic hydrocarbon group Zhiji 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 one 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, norbornane, isobornane, 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 haloalkyl 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 haloalkyl group as the substituent include a group in which part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms. Part of the carbon atoms constituting the ring structure of the cyclic aliphatic hydrocarbon group may be substituted with substituents containing heteroatoms. 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 heterocyclic rings in which part of the carbon atoms constituting the aromatic hydrocarbon ring are substituted 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 formed by removing two hydrogen atoms from aromatic compounds with an aromatic ring (such as biphenyl, fluorine, etc.); a group formed by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl or A heteroaryl group in which one hydrogen atom is substituted by an alkylene group (for example, from benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2- A group formed by removing one hydrogen atom from the aryl group in an arylalkyl group such as naphthylethyl), etc. The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the above-mentioned aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted as a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl 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 haloalkyl group as the substituent include those exemplified as the substituent 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 be substituted with an alkane group, acyl group and other substituents), -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 -OC The group represented by (=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, and O is 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 with substituents such as alkyl and hydroxyl groups. 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 that 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 base 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, especially preferably 1. That is, as the base represented by the formula -[Y ²¹ -C(=O)-O] _m'' -Y ²² -, a base 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 heterocyclic rings in which part of the carbon atoms constituting the aromatic hydrocarbon ring are substituted 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 still 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 mixtures thereof. With e.g. ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dihydroxy Polyester polyol obtained by reacting methylheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol and other glycols 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 polyether polyols include: using low-weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as starters to prepare ethylene oxide, propylene oxide, butylene oxide, etc. Polyether polyol obtained by polymerizing alkylene oxide compounds such as alkanes and tetrahydrofuran.

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 produced by using aliphatic diamines having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine, etc. as raw materials in the above-mentioned esterification reaction. The obtained polyesteramide polyol.

Examples of the acrylic polyol include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc. containing one or more hydroxyl groups in one molecule, or their corresponding methacrylic acid derivatives, etc. Polyesteramide polyol obtained by copolymerizing with, for example, acrylic acid, methacrylic acid or their esters.

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

The polyurethane polyol is a polyol having one or more urethane bonds per molecule. Examples thereof include polyether polyols and polyesters having a number average molecular weight of 200 to 20,000. Polyurethane polyol obtained by reacting polyol, polyetherester 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 Preferably it is 0.3-3, More preferably, 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, from the viewpoint of adjusting the viscosity of the adhesive composition and the hardness of the adhesive layer, polycarbonate polyol and low molecular polyol are preferred as the (O2) component. In addition, from the viewpoint of improving the heat resistance of the adhesive layer, castor oil-modified polyol may be used as the (O2) component.

From the viewpoint of adjusting the viscosity of the adhesive composition and the heat resistance of the adhesive layer, the (O) component is preferably a combination of the (O1) component and the (O2) component. 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, preferably 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 isocyanato 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 that absorbs 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) includes a structure that absorbs 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 that absorbs 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 fused ring skeleton contains a fused 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 fused ring may be composed only of an aromatic ring, or may be a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, but is preferably a fused 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 that absorbs at least part of the light in the range of 300 to 800 nm wavelength; 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 or different from each other. In the formula (u1-2), X ² is a 1-valent group containing a structure that absorbs 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 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 ² may be the same as 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 above-mentioned aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. 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 still more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, and more preferably has 3 to 6 carbon atoms. The aliphatic hydrocarbon group mentioned above may have a substituent. The above-mentioned substituent may be a substitute for a hydrogen atom, or may be a substitute for a methylene group (-CH ₂ -) in the carbon chain. Examples of those 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 linked. The above aromatic hydrocarbon group may have a substituent. The above substituent may be one that substitutes a hydrogen atom of the aromatic ring, or one that substitutes a hetero atom with a carbon atom constituting the ring of 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 above-mentioned aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. 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 still more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, and more preferably has 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 linked. 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 ring of 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 that may have a substituent, more preferably a saturated aliphatic hydrocarbon group that may have a substituent, and even more preferably a saturated aliphatic hydrocarbon group that does not have a substituent, especially linear or branched. The alkyl group. The number of carbon atoms of the 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 an n1 valence group including a structure (structure X) that absorbs at least part of the light in the range of 300 to 800 nm wavelength. Examples of X ¹ include an n1 valent group containing a group including an aromatic fused ring skeleton, a benzophenone skeleton, a benzoylmethane skeleton, a benzoylbenzene skeleton, or a benzotriazole skeleton. . In the general formula (u1-2), X ² is a 1-valent group including a structure (structure X) that absorbs at least part of the light in the range of 300 to 800 nm wavelength. Examples of X ² include a monovalent group containing a group including an aromatic fused ring skeleton, a benzophenone skeleton, a benzoylmethane skeleton, a benzoylbenzene skeleton, or a benzotriazole skeleton. .

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 ⁾ , Branched alkyl group; n1 is an integer from 2 to 4. The plural Y ^11's may be the same or different from each other. The plural L ¹¹ may be the same as or different from each other. ^In Formula ⁽ u1-2-1 ⁾ , Chain 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. The plural L ²¹ may be the same as 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 a plurality of L ^a1 and L ^a2 which may be the same or different from each other. When m is 2 or more, there are a plurality of 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 above-mentioned aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is preferably a saturated hydrocarbon group. 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 still more preferably 2 or 3 carbon atoms. The aliphatic hydrocarbon group containing a ring structure preferably has 3 to 10 carbon atoms, and more preferably has 3 to 6 carbon atoms. The aliphatic hydrocarbon group mentioned above may have a substituent. The above-mentioned substituent may be a substitute for a hydrogen atom, or may be a substitute for 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 linked. The above aromatic hydrocarbon group may have a substituent. The above substituent may be one that substitutes a hydrogen atom of the aromatic ring, or one that substitutes a hetero atom with a carbon atom constituting the ring of 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, and more preferably have 1 to 3 carbon atoms. The alicyclic group preferably has 1 to 6 carbon atoms. Examples of the nitrile alkyl group include a malonitrile group. The alicyclic group may be an alicyclic hydrocarbon ring or an alicyclic heterocyclic ring. Examples of the alicyclic heterocyclic ring include those containing a sulfur atom, a nitrogen atom, or an oxygen atom. Specific examples of the alicyclic heterocyclic ring include dithiophene.

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 a plurality of 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 linking group include the same linking 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 substituted with -O-, -CO-, -NH-, -COO-, -CONH- is an alkyl group.

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 substituted with -O-, -CO-, -NH-, -COO-, -CONH- is an alkyl group.

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 benzene skeleton include those 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 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 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 substituted with -O-, -CO-, -NH-, -COO-, -CONH- is an alkyl group.

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, 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 a plurality of 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 linking group include the same linking 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, and is 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. The alkyl group which may have a substituent and the alkyl group bonded to a benzene ring preferably have 1 to 5 carbon atoms, and more preferably have 1 to 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 them.

[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 20 mass % relative to the mass of all the monomers (100 mass %). Quality% or more. When the ratio of the component (U1) is equal to or higher than the above-mentioned preferable lower limit, the separation performance becomes 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% or less based on the mass of all monomers (100 mass%). , 55 mass% or less, or 50 mass% or less. If the ratio of the component (U1) is below the above-mentioned preferred upper limit, balance with other monomers can be easily achieved.

When the component (P1) is a urethane resin, the component (P1) can be synthesized by mixing the component (I), the component (O), and the component (U1), and mixing them according to a known amine method. The synthesis method of methyl formate resin is copolymerization. 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-tolyl)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 "Perocta" manufactured by Nippon Oils and Fats Co., Ltd. can be used (Registered Trademark)" and other commercially available products.

Examples of azo polymerization initiators among thermal polymerization initiators include: 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1 ,1'-Azo(methylethyl)diacetate, 2,2'-Azobis(2-amidinopropane) hydrochloride, 2,2'-Azobis(2-aminopropane) ) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis -Methyl 2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, 2,2'- Dimethyl azobisisobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sodium sulfonate), 2-(4-methylphenylazo)-2-methyl Malononitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 2,2'-azobis- 2-Methylvaleronitrile, 4,4'-azobis-4-cyanovalerate 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, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane , phenyl azotriphenylmethane, 4-nitrophenyl azotriphenylmethane, 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-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl Oxy)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-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- Carbazol-3-yl]ethanone-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-dimethylaminobenzoic acid Butyl ester, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl ketal, benzyl Benzodimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-phenyl benzoate, 2,4-diethyl 9 -oxygen sulfur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-mercaptobenzoxazole, 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, benzil, benzil benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, benzoin Ethyl ketone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylbenzene Ethyl ketone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone , 9-oxysulfur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-methoxytriazine, 2,4,6-tris(trichloromethyl)s-triazine, 2- Methyl-4,6-bis(trichloromethyl)s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)s-triazine Triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)s-triazine, 2-[2-(4-diethylamino-2- Methylphenyl)vinyl]-4,6-bis(trichloromethyl)s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis (Trichloromethyl)s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)s-triazine, 2-(4-ethoxystyryl)- 4,6-bis(trichloromethyl)s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)s-triazine, 2,4-bis-triazine Chloromethyl-6-(3-bromo-4-methoxy)phenyls-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyls-triazine Triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-( 2-Bromo-4-methoxy)styrylphenyl-s-triazine, 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) 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＞ The adhesive composition of this embodiment may contain optional components in addition to the above-mentioned components within a range that does not impair the effects of the present invention. The optional components are not particularly limited, and examples thereof include polymerization inhibitors, solvent components, plasticizers, adhesion auxiliaries, stabilizers, colorants, surfactants, and the like.

"Polymerization Inhibitor" Polymerization inhibitors refer to components that have the function of preventing radical polymerization reactions caused by heat and light. Polymerization inhibitors show high reactivity towards free radicals.

As a polymerization inhibitor, one preferably has a phenol skeleton. For example, hindered phenol antioxidants can be used as the polymerization inhibitor, and examples include: pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methyl p- Hydroquinone, pentoquinone, pentyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methyl) phenol), 4,4'-(1-methylethylidene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl) )-1-methylethyl)phenyl]ethylidene]bisphenol, 4,4',4''-ethylidene tris(2-methylphenol), 4,4',4''-ethylene Ethyltriphenol, 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) isocyanate Urea ester, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc.

A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the polymerization inhibitor may 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 components as needed in a solvent component and mixing them. As the solvent component, a solvent component 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, Branched-chain hydrocarbons such as isononane and isododecane; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, and birthane , norbornane, pinane, thujane, carane, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, Alicyclic hydrocarbons such as α-thujone, β-thujone, cyclohexane, cycloheptane, and cyclooctane; toluene, xylene, indene, cyclopentadiene, indane, tetrahydroindene, naphthalene , tetralin (tetralin), decalin (decalin) and other aromatic hydrocarbons.

Petroleum-based solvents refer to solvents purified from heavy oil. Examples include white kerosene, paraffin-based solvents, and isoalkane-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-caseinol, 1,8-caseinone, borneol, cyprione, 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 groups such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc. of the above-mentioned polyols or the above-mentioned compounds with ester bonds. Derivatives of polyols such as compounds with ether bonds such as ether or monophenyl ether (among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); Cyclic ethers such as dioxane; methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate Esters such as ethyl ethoxypropionate and ethyl ethoxypropionate; aromatic compounds such as anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butyl phenyl ether, etc. It is an organic solvent.

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 inactive with respect to the component (P1) is preferred. Preferred 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% relative to the total amount of the adhesive composition (100 mass%). That is, in the adhesive composition of this embodiment, the concentration of the solid content (total amount of ingredients other than the solvent component) 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 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 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, the resin (P1) contained in the adhesive layer that temporarily adheres a semiconductor substrate or the like to a support contains a structure When the adhesive layer is irradiated with light such as laser light, the structure X in the adhesive layer absorbs the light, causing the adhesive layer to change in quality. Thereby, the adhesive force of the adhesive layer is reduced, and the semiconductor substrate etc. can be separated from the support. Therefore, no separation layer is required. Furthermore, since the structure X is incorporated into the component (P1), solubility does not become a problem, and the content ratio of the structure X can be increased. By this, good separability can be obtained. Furthermore, the storage modulus (G') at 150°C of the adhesive composition layer formed from the adhesive composition of this embodiment is 1.5×10 ⁵ Pa or less. Therefore, the adhesion between the semiconductor substrate and the support becomes good.

When the resin (P1) is a thermosetting resin, an adhesive composition layer is formed between the semiconductor substrate, etc. and the support, and is cured. Thereby, an adhesive layer is formed 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 above). Therefore, even when semiconductor substrates or electronic devices are processed at high temperatures, defects such as positional deviation and sinking are less likely to occur. Furthermore, when the resin (P1) is a urethane resin, the adhesive layer can be decomposed by decomposing the urethane bond using an acid or a base. Therefore, even when 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 cleaning 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 combination of the first aspect. The hardened body of things.

FIG. 1 shows one embodiment of the laminate of the second aspect. The laminated body 100 shown in FIG. 1 includes a light-transmitting support 1, 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 aspect. 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 yet another embodiment of the laminate of the second aspect. 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 yet another embodiment of the laminate of the second aspect. 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 the semiconductor substrate or electronic device. The support has light-transmitting properties. The support is bonded to the semiconductor substrate or 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 the 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 a large panel that is made by enlarging the size of a circular support and has a quadrilateral shape when viewed from above.

＜Adhering layer＞ The subsequent layers are provided to temporarily bond the semiconductor substrate or electronic device to the support. The adhesive layer is formed from the adhesive composition of the above-mentioned first embodiment. When the component (P1) is a thermosetting resin, the adhesive layer is a cured body of the component (P1). When the component (P1) is a thermosetting resin, the adhesive composition 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, and more preferably in the range of 5 μm or more and 150 μm or less.

When the adhesive layer is a cured body of thermosetting resin, the material (cured body) constituting the adhesive layer preferably satisfies the following characteristics. When the complex elastic modulus of the hardened body 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. Furthermore, when the complex elastic modulus of the hardened body 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 body 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 PET film peeling test piece (size 5 mm × 40 mm, thickness 50 μm) was measured using the above measuring device. As far as the measurement conditions are concerned, the following conditions can be adopted: under the tensile condition 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 bonded to the support via the bonding 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 device as exemplified in the above-mentioned “(adhesive composition)” can be exemplified. The electronic device is preferably a composite of a member made of metal or a semiconductor and a resin that seals or insulates the member. Specifically, the electronic device includes at least one of a sealing material layer and a wiring layer, and may also include a semiconductor substrate. In the laminated body 200 shown in FIG. 2 , the electronic device 456 is composed of the semiconductor substrate 4 , the sealing material layer 5 , and the wiring layer 6 . In the laminated body 300 shown in FIG. 3 , the electronic device 6 is composed of the wiring layer 6 . In the laminated body 400 shown in FIG. 4 , the electronic device 645 is composed of 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 composed of 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. Sealing materials may contain other ingredients such as fillers in addition to resin. Examples of the filler include spherical silica particles.

"Wiring Layer" The wiring layer is also called RDL (Redistribution Layer). It is a wiring body that constitutes a thin film of wiring connected to the substrate. It can have a single-layer or multiple-layer structure. The wiring layer may be a conductor (such as metals such as aluminum, copper, titanium, nickel, gold, and silver, and a silver-tin alloy) between dielectrics (silicon oxide (SiO _x ), photosensitive resins such as photosensitive epoxide, etc.) alloy) formed with wiring, 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 can be made of light-transmitting materials. Thereby, it is possible to appropriately add a layer that imparts better properties to the laminated bodies 100 to 400 without preventing light from entering the adhesive layer 3 . Depending on the type of material constituting the adhesive layer 3, the wavelength of light that can be used varies. Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from materials that can transmit light of wavelengths that can cause the material constituting the adhesive layer 3 to deteriorate.

(Manufacturing method of laminated body (1)) The method for manufacturing a laminated body according to the 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, and the manufacturing method has the following steps: The step of coating the adhesive composition of the first aspect on a support or a 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 hardening the above-mentioned adhesive composition layer through the polymerization reaction of the above-mentioned urethane resin and the step of forming the above-mentioned 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 an adhesive composition layer forming step. 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 forming 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 of applying an adhesive composition 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 formation method of forming the adhesive composition layer 3' on the support 1 is not particularly limited, and examples thereof include spin coating, dipping, roller knife coating, spray coating, slit coating, and other methods. The adhesive composition layer can also be formed on the semiconductor substrate 4 by the same method.

After forming the adhesive composition layer, baking processing may also 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 at a temperature of 70 to 100° C. for 1 to 10 minutes may be used.

[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 mounting the semiconductor substrate 4 on the support 1 via the adhesive composition layer 3' is not particularly limited, and a method generally used for arranging the semiconductor substrate at a predetermined position can be used.

[Subsequent layer formation step] When the component (P1) is a thermosetting resin, the manufacturing method of the laminated body of this embodiment may include an adhesive layer forming step. The subsequent layer forming step is a step in which the adhesive composition layer is hardened by a curing reaction of the component (P1) in the adhesive composition layer to form an 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 ′.

When the component (P1) contains a polymerizable carbon-carbon double bond, an appropriate method can be selected according to the type of the polymerizable carbon-carbon double bond to perform the polymerization reaction, thereby performing the hardening reaction of 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.

By this step, the (P1) component in the adhesive composition layer 3' is hardened, and the adhesive layer 3 which is the hardened body of the adhesive composition layer 3' is formed. Thereby, the support 1 and the semiconductor substrate 4 are temporarily connected. As a result, the laminated body 100 can be obtained.

[optional step] The manufacturing method of the laminated body of this embodiment may include other steps in addition to the above-mentioned steps. As other steps, for example, various mechanical treatments or chemical treatments (grinding, chemical mechanical polishing (CMP) and other thin film treatments; chemical vapor deposition (CVD), physical vapor deposition (PVD), etc. under high temperature and vacuum) can be cited. Treatment; treatment using chemicals such as organic solvents, acidic treatment solutions, alkaline treatment solutions; electroplating treatment; irradiation of active light; heating, cooling treatment, etc.), 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 above-mentioned third aspect, there is further an electronic device forming step of forming an electronic device, and the electronic device is: A composite of a component made of metal or semiconductor 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 formation steps] 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 made of 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, for example, a sealing material heated to 130 to 170° C. is supplied to the adhesive layer 3 to cover the semiconductor substrate 4 while maintaining a high viscosity state, and is formed on the adhesive layer by pressure molding. 3, a laminate 110 with a sealing material layer 5 is provided. 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. For example, as shown in FIG. 7( b ), the sealing material portion is ground by grinding the sealing material layer 5 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, the following method can be mentioned, for example. First, a dielectric layer of silicon oxide (SiO _x ), photosensitive resin, or the like 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 applying 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, wiring is formed on the dielectric layer using a conductor such as metal. As a method of forming the wiring, for example, known semiconductor manufacturing methods such as photolithography (resist photolithography) and etching can be used. Examples of such photolithography processing include photolithography processing using a positive resist material and photolithography processing 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: on the support, The step of applying the adhesive composition of the first aspect 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 electronic device is a composite of a member made of metal or a semiconductor 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) ).

Similar to the manufacturing method of the fourth aspect, the laminated body obtained by the manufacturing method of the laminated body of this embodiment is a laminated body in which a support, an adhesive layer, and an electronic device are laminated in this order.

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 above-mentioned 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 in which the semiconductor substrate is sealed with a sealing material on a support via an adhesive composition layer.

The subsequent layer formation step can be performed in the same manner as in the method for manufacturing a laminated body according to the third aspect.

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

According to the manufacturing method of the laminated body of the above-mentioned third to fifth aspects, since the support and the semiconductor substrate or electronic device are temporarily bonded via the highly heat-resistant adhesive layer, it is possible to stably manufacture the support and the bonding layer sequentially. , and laminates made of semiconductor substrates or electronic devices. The above-described laminate system is a laminate produced in a process based on fan-out technology, which mounts terminals provided on a semiconductor substrate on a wiring layer that extends out of 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 by the method for manufacturing a laminated body according to any one of the above-mentioned third to fifth aspects, it has the following step: passing the support through the A step of irradiating the above-mentioned adhesive layer with light to alter the quality of the above-mentioned adhesive layer, thereby separating the above-mentioned electronic device from the above-mentioned support (hereinafter also referred to as a "separation step"); and using an acid or alkali to remove the amine in the above-mentioned adhesive layer. The step of removing the above-mentioned adhesive layer by decomposing the urethane ester bond (hereinafter also referred to as the "adhesive layer removal step").

8 is a schematic step diagram illustrating one embodiment of a method of manufacturing 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 the adhesive layer 3 with light (arrow) through the support 1 to change the quality of 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 light-transmitting support 1 , thereby degrading the adhesive layer 3 .

The wavelength of the light used in the separation step can be selected based on the wavelength of light 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 laser light such as YAG laser light, ruby laser light, glass laser light, YVO ₄ laser light, LD laser light, and fiber laser light can be used. , liquid laser light such as pigment laser light, CO ₂ laser light, excimer laser light, Ar laser light, He-Ne laser light and other gas laser light, semiconductor laser light, free electron laser light and other laser light, non-laser light. Thereby, the adhesive layer 3 can be changed into a state in which 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 from 20 kHz to 60 kHz, and more preferably from 30 kHz to 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 in a direction in which the support 1 and the electronic device 456 are separated from each other. Specifically, with one of the support 1 or the electronic device 456 side (wiring layer 6) fixed to the platform, the other is adsorbed and held on a separation plate equipped with an adsorption pad such as a bellows pad. Lift up at the same time, whereby the support 1 and the electronic device 456 can be separated. 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 it is a laminated body with a diameter of about 300 mm, it can be applied 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 method of manufacturing an electronic component according to this embodiment includes an adhesive layer removal step. The method of removing the adhesive layer is not particularly limited and can be appropriately selected depending on the type of component (P1). For example, when the component (P1) is a urethane resin, the urethane bond can be decomposed using an acid or a base to remove the adhesive layer. Alternatively, an appropriate adhesive stripping liquid can be used to remove the 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 removed by decomposition and/or peeling of the adhesive layer 3 to obtain the electronic component 50 .

When the component (P1) is a urethane resin, the adhesive layer 3 contains a urethane resin formed by copolymerization of the above-mentioned component (I) and (O) component, or a urethane resin formed by the copolymerization of the above-mentioned (P1) component. ) cross-linked urethane resin formed by the polymerization of components. When these urethane resins are treated with an acid or an alkali, the urethane bond is cut and decomposed. 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 for decomposing the urethane bond is not particularly limited. 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 inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine, but are not limited thereto. .

The above-mentioned acid or alkali can be dissolved in a solvent and used in the form of a treatment liquid for removing the adhesive layer. As the above-mentioned solvent, a polar solvent is preferred, and examples thereof include dimethylsulphite (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 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. In addition, the content of the polar solvent in the above-mentioned treatment liquid may be, for example, 50 to 99% by mass. As the treatment liquid for removing the adhesive layer, a commercially available alkaline treatment liquid or acidic treatment liquid 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 according to this embodiment, after the above-described step of removing the adhesive layer, the electronic component 50 may be further subjected to processes such as solder ball formation, cutting, or oxide film formation.

According to the manufacturing method of electronic parts of this embodiment, the resin (P1) has the structural unit (u1) including a structure (structure X) that absorbs at least part of the light in the range of 300 to 800 nm wavelength. The light will cause the adhesion layer to deteriorate, causing the adhesion strength to decrease. Therefore, even if there is no separation layer, it is possible to easily separate the temporarily bonded semiconductor substrate and the like from the support. Structure X is incorporated in the form of a structural unit of resin (P1). Therefore, the content of structure X can be increased while maintaining good adhesion. In this way, good adhesion and separation can be achieved at the same time. Furthermore, when the component (P1) is a urethane resin, the residue of the adhesive layer attached to the semiconductor substrate or the like separated from the self-supporting body can be obtained by decomposing the urethane bond using an acid or a base. Removes easily. 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 Urethane Resin: Urethane 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. parts, 13 parts of glycerol monoacrylate, 20 parts of monomer (T-33), and polymerization inhibitor, and mix them uniformly under nitrogen flow. Then, 35 parts of isophorone diisocyanate was added to the dropping funnel and added dropwise at a uniform rate over 30 minutes. After the dropwise addition, aging was performed for 30 minutes. Then, add a bismuth catalyst, raise the temperature to 65°C, and perform aging 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 urethane resin (P1-1) was 15,800. The C=C equivalent (molecular weight per 1 equivalent of polymerizable carbon-carbon double bonds of the urethane resin) of the urethane resin (P1-1) is 1230 g/eq.

<Synthesis Example 2 of Urethane Resin: Urethane Resin (P1-2)> Urethane resin (P1-2) was synthesized by the same method as 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 urethane resin (P1-2) was 32,000. The C=C equivalent (molecular weight of polymerizable carbon-carbon double bonds per 1 equivalent of urethane resin) of urethane resin (P1-2) is 1230 g/eq.

<Synthesis example 3 of urethane resin: urethane resin (P1-3)> Urethane resin (P1-3) was synthesized by the same method as 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 urethane resin (P1-3) was 33,200. The C=C equivalent (molecular weight of polymerizable carbon-carbon double bonds per 1 equivalent of urethane resin) of urethane resin (P1-3) is 1230 g/eq.

<Synthesis Example 4 of Urethane Resin: Urethane Resin (P2-1)> Urethane resin (P2-1) was synthesized by the same method as 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 urethane resin (P2-1) was 16,000. The C=C equivalent (molecular weight of polymerizable carbon-carbon double bonds per 1 equivalent of urethane resin) of urethane 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%)

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

[Chemical 12]

Polycarbonate diol (long chain): Polycarbonate diol represented by the following formula (PC-1-1) (R=-(CH ₂ ) ₆ -, -(CH ₂ ) ₅ -), 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 Examples 1 to 2) The ingredients shown in Table 2 were mixed to prepare adhesive compositions for each example.

[Table 2] (P1)Ingredients (A)Ingredients (Ad)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] Comparative example 2 (P2)-2 [100] - (Ad)-1 [1] (S)-2 [376]

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 urethane resins (P1-1) to (P1-3) synthesized in the above synthesis examples 1 to 3. (P2)-1: The urethane resin (P2-1) synthesized in the above-mentioned Synthesis Example 4. (P2)-2: Septon8004 (trade name), manufactured by KURARAY Co., Ltd. The styrene content is 12 mol% and the weight average molecular weight is 98,000; it is an elastomer with multiple structural units represented by the following chemical formula.

[Chemical 16]

(A)-1: Peroxide (Percumyl (registered trademark) D, Nippon Oils and Fats Co., Ltd.). Bis(1-methyl-1-phenylethyl) peroxide (Ad)-1: Polymerization inhibitor. IRGANOX1010 (trade name), manufactured by BASF. Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (S)-1: PGMEA. (S)-2: Decalin.

[Measurement of storage modulus (G')] The adhesive composition of each example was coated on the PET film with the release agent, and heated at 50°C and 100°C for 60 minutes each in an atmospheric pressure oven to form an adhesive composition layer (thickness: 0.5 mm). Next, the storage modulus (G′) at 150°C was measured using a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM Co., Ltd.) for the adhesive composition layer peeled off from the PET film. Regarding the measurement conditions, the following conditions were set: the sample shape of the adhesive composition layer was 2.5 mm × 2.5 mm × 0.5 mm, and the temperature was raised from room temperature to 215°C at a rate of 5°C/min under shear conditions with a frequency of 1 Hz. ℃, the storage modulus (G') was measured.

＜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. Then, use a die bonder (manufactured by TRESKY) to heat the plate of the die bonder to 50°C, and press the above-mentioned bare chip through the above-mentioned bonding layer under the conditions of 350 g 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 adhesion] A laminated body was produced as described above, and the adhesion between the bare wafer and the bare glass support was evaluated. The adhesive properties are evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3. Evaluation benchmark ○: The bare chip and the bare glass support can be bonded together. ×: The bare chip cannot be bonded to the bare glass support.

[Evaluation of separation] Using IPEX848 (308 nm XeCl, LightMachinery), under the conditions of a scanning speed of 15.6 mm/second (overlap 80%), a frequency of 60 kHz, and a beam size of 2×14 mm, automatic The bare glass support side of the above-mentioned laminate is irradiated with laser light having a wavelength of 308 nm toward the above-mentioned adhesive layer. Then, I tried peeling off the bare glass. Separability was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3. Evaluation criteria ○: 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] Storage modulus (Pa) Continuity Separation Example 1 2.1×10 ² ○ ○ Example 2 2.5×10 ² ○ ○ Example 3 4.7×10 ○ ○ Comparative example 1 2.0×10 ² ○ × Comparative example 2 2.3×10 ⁵ × -

From the results shown in Table 3, it was confirmed that the adhesive layer formed using the adhesive compositions of Examples 1 to 3 had good adhesiveness and also functioned 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 one embodiment of a laminated body to which the present invention is applied. FIG. 2 is a schematic diagram showing one embodiment of a laminated body to which the present invention is applied. FIG. 3 is a schematic diagram showing one embodiment of a laminated body to which the present invention is applied. FIG. 4 is a schematic diagram showing one 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 a 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 (7)

An adhesive composition for forming an adhesive layer that temporarily connects a semiconductor substrate or electronic device to a light-transmitting support. The adhesive composition contains: resin (P1), and polymerization initiator (A) ), the above-mentioned resin (P1) has a structural unit (u1) including a structure that absorbs at least part of the light in the range of 300 to 800 nm wavelength, the adhesive composition layer formed from the above-mentioned adhesive composition is stored at 150°C The module (G') is 1.5×10 ⁵ Pa or less. The adhesive composition of claim 1, wherein the above-mentioned structural unit (u1) includes an aromatic fused ring skeleton, a benzophenone skeleton, a diphenylmethane skeleton, a diphenylbenzene skeleton, or a benzotribenzene skeleton. Azole skeleton. The adhesive composition according to claim 1 or 2, wherein a composite of a member made of 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. A laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device are laminated in this order. The above-mentioned adhesive layer is a hardened body of the adhesive composition according to any one of claims 1 to 3. A method of manufacturing a laminated body, which is a method of manufacturing a laminated body in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are sequentially laminated. The manufacturing method of the laminated body has 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 light-transmitting support, an adhesive layer, and an electronic device are sequentially laminated. After the laminated body is obtained by the method for manufacturing a laminated body according to Claim 5, there is further a step of forming an electronic device, which is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. A manufacturing method of electronic components, which has the following steps after obtaining the laminated body by the manufacturing method of the laminated body according to claim 6: The step of irradiating the adhesive layer with light through the support to modify the adhesive layer, thereby separating the electronic device from the support; and The step of removing the above-mentioned adhesive layer attached to the above-mentioned electronic device.