JP2021107523A - Adhesive composition, laminate, method for manufacturing laminate and method for manufacturing electronic component - Google Patents

Abstract

To provide: an adhesive composition having high heat resistance and capable of easily removing an adhesive layer; a laminate manufactured using the adhesive composition; a method for manufacturing the laminate; and a method for manufacturing an electronic component using the adhesive composition.SOLUTION: An adhesive composition used for forming an adhesive layer capable of temporarily bonding a semiconductor substrate or an electronic device to a support comprises: an urethane resin including a polymerizable carbon-carbon double bond; and a polymerization initiator.SELECTED DRAWING: None

Description

The present invention relates to an adhesive composition, a laminate, a method for producing a laminate, and a method for producing an electronic component.

The semiconductor package (electronic component) including the semiconductor element has various forms depending on the corresponding size, and includes, for example, WLP (Wafer Level Package), PLP (Panel Level Package) and the like.
Examples of semiconductor package technology include fan-in type technology and fan-out type technology. As a semiconductor package based on the fan-in type technology, a fan-in type WLP (Fan-in Wafer Level Package) or the like in which the terminals at the end of the bare chip are rearranged in the chip area is known. As a semiconductor package based on the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package) or the like in which the terminals are rearranged outside the chip area is known.

In recent years, in particular, fan-out type technology has been applied to fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged and packaged on a panel. It is attracting attention as a method that can realize thinning and miniaturization.

In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the element to be incorporated. However, if the thickness of the substrate is reduced, the strength of the substrate is reduced, and the substrate is liable to be damaged during the manufacture of the semiconductor package. On the other hand, there is known a technique of temporarily adhering a substrate to a support using an adhesive, processing the substrate, and then separating the substrate and the support.

As the adhesive used for temporary bonding between the substrate and the support, a thermoplastic adhesive is often used because the adhesive layer can be easily removed with a solvent or the like. For example, Patent Document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high boiling point solvent, and a low boiling point solvent.

International Publication No. 2016/05/2315

By the way, in semiconductor package manufacturing, high temperature treatment such as thin film formation, firing, and die bonding may be performed. If the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer decreases during high-temperature treatment, and there is a concern that the substrate may be misaligned or the substrate may sink. On the other hand, if the heat resistance of the adhesive is increased, the applicability to the substrate or the support tends to decrease.
When a thermosetting adhesive is used to bond the support and the substrate, problems such as misalignment and sinking do not occur during high temperature treatment. However, it is difficult to remove the adhesive layer with a solvent or the like, and even when the separation layer is provided, it is difficult to remove the adhesive layer adhering to the substrate after separating the support and the substrate due to the deterioration of the separation layer.
The present invention has been made in view of the above circumstances, and is an adhesive composition having high heat resistance and easy removal of an adhesive layer, a laminate produced by using the adhesive composition, and the laminate. It is an object of the present invention to provide a method for producing an electronic component using the adhesive composition.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support, and is a polymerizable carbon-carbon double bond. An adhesive composition containing a urethane resin containing the above and a polymerization initiator.

A second aspect of the present invention is a laminate in which a support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, and the adhesive layer is a curing of the adhesive composition according to the first aspect. It is a body, a laminated body.

A third aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, and the adhesive composition according to the first aspect is applied to the support or the semiconductor substrate. To form an adhesive composition layer, a step of placing the semiconductor substrate on the support via the adhesive composition layer, and a polymerization reaction of the urethane resin. A method for producing a laminated body, which comprises a step of curing an adhesive composition layer to form the adhesive layer.

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

In a fifth aspect of the present invention, the adhesive layer is removed by decomposing the urethane bond of the urethane resin with an acid or an alkali after obtaining the laminate by the method for producing a laminate according to the fourth aspect. It is a method of manufacturing an electronic part having a step of performing.

According to the present invention, an adhesive composition having high heat resistance and easy removal of an adhesive layer, a laminate produced using the adhesive composition, a method for producing the laminate, and the adhesive composition. A method for manufacturing an electronic component using an object is provided.

It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic process diagram explaining one Embodiment of the manufacturing method of the laminated body 100'in which a support, an adhesive composition layer, and a semiconductor substrate are laminated in this order. 5 (a) is a diagram showing a support composed of a support substrate and a separation layer, FIG. 5 (b) is a diagram for explaining an adhesive composition layer forming step, and FIG. 5 (c) is a diagram for explaining an adhesive composition layer forming step. It is a figure explaining the semiconductor substrate mounting process. It is a figure explaining the adhesive layer forming process. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a laminated body 120. FIG. 7A is a diagram for explaining a sealing process, FIG. 7B is a diagram for explaining a grinding process, and FIG. 7C is a diagram for explaining a wiring layer forming process. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a semiconductor package (electronic component) from a laminated body 120. 8 (a) is a diagram showing the laminated body 200, FIG. 8 (b) is a diagram for explaining a separation step, and FIG. 8 (c) is a diagram for explaining an adhesive layer removing step.

In the present specification and claims, "aliphatic" is defined as a concept relative to aromatics and means a group, a compound or the like having no aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" shall include linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of hydrogen atoms of an alkyl group or an alkylene group is substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When describing "may have a substituent" or "may have a substituent", the case where the hydrogen atom (-H) is substituted with a monovalent group and the case where the methylene group (-CH _{2) is substituted.} Includes both cases where −) is replaced with a divalent group.
"Exposure" is a concept that includes general irradiation of radiation.

The “constituent unit derived from hydroxystyrene” means a structural unit formed by cleaving the ethylenic double bond of hydroxystyrene. The “constituent unit derived from the hydroxystyrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the hydroxystyrene derivative.
The "hydroxystyrene derivative" is a concept including a hydrogen atom at the α-position of hydroxystyrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent. The hydrogen atom of the hydroxyl group of hydroxystyrene is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group is bonded to a good hydroxystyrene benzene ring. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of hydroxystyrene include those similar to those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom. Be done. 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 preferable.
Further, as the hydroxyalkyl group as the substituent at the α-position, specifically, a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a hydroxyl group can be mentioned. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

In the present specification and claims, some structures represented by chemical formulas have asymmetric carbons, and enantiomers and diastereomers may be present. In the case, one formula is used to represent those isomers. These isomers may be used alone or as a mixture.

(Adhesive composition)
The adhesive composition according to the first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support, and is a polymerizable carbon-. It is characterized by containing a urethane resin containing a carbon double bond and a polymerization initiator.

<Target of temporary adhesion>
The adhesive composition according to this embodiment is used to form an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support. As used herein, "temporary bonding" means that the objects to be bonded are temporarily bonded (for example, during an arbitrary work process). More specifically, the semiconductor substrate or the electronic device is temporarily adhered to the support and fixed on the support for the purpose of thinning the device, transporting the semiconductor substrate, mounting on the semiconductor substrate, and the like (provisional). Adhesion), separated from the support after the process is complete.

≪Semiconductor substrate≫
The semiconductor substrate to which the adhesive composition according to this embodiment is applied is not particularly limited, and may be generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is subjected to processes such as thinning and mounting while being supported by a support. Structures such as integrated circuits and metal bumps may be mounted on the semiconductor substrate.
The semiconductor substrate is typically a silicon wafer substrate, but is not limited to this, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like. Further, the semiconductor substrate may be a resin substrate such as a mold substrate. Examples of the resin constituting the resin substrate include epoxy-based resin and silicone-based resin.

≪Electronic device≫
As used herein, the term "electronic device" means a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited, and various mechanical structures and circuits may be formed on the surface of the semiconductor substrate. The electronic device may preferably be a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. The electronic device may have a rewiring layer described later and / or a semiconductor element or other element sealed or insulated with a sealing material or an insulating material, and has a single-layer or multi-layer structure. obtain.

≪Support≫
The support is a member that supports a semiconductor substrate or an electronic device. As will be described later, the support may be composed of a support substrate which has a property of transmitting light and is a member for supporting the semiconductor substrate, and a separation layer which is altered by irradiation with light.

<Urethane resin containing polymerizable carbon-carbon double bond: (P1) component>
The adhesive composition according to the present embodiment contains a urethane resin containing a polymerizable carbon-carbon double bond (hereinafter, also referred to as “(P1) component”). The component (P1) can be polymerized and cured by a polymerizable carbon-carbon double bond to form an adhesive layer. As a result, the semiconductor substrate or electronic device and the support can be temporarily bonded. Further, the urethane bond in the component (P1) has a property of being decomposed by an acid or an alkali. Therefore, the adhesive layer can be easily removed by a treatment liquid containing an acid or an alkali.

The polymerizable carbon-carbon double bond contained in the component (P1) is not particularly limited, but is preferably radically polymerizable. Examples of the polymerizable carbon-carbon double bond include a methacryloyl group and an acryloyl group. The polymerizable carbon-carbon double bond contained in the component (P1) may be one kind or two or more kinds.
The equivalent of the polymerizable carbon-carbon double bond contained in the component (P1) is 200 to 2000 g / eq. The above is preferable, and 300 to 1500 g / eq. The above is more preferable, and 400 to 1200 g / eq. The above is more preferable, and 500 to 1000 g / eq. Is particularly preferable. When the polymerizable carbon-carbon double bond equivalent is at least the lower limit of the preferable range, the elastic modulus, heat resistance, etc. of the adhesive layer are further improved. When the polymerizable carbon-carbon double bond equivalent is not more than the upper limit of the above-mentioned preferable range, the adhesive layer does not become too hard and the detergency becomes good. The equivalent number is the molecular weight of the urethane resin per equivalent of the polymerizable carbon-carbon double 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, and 13,000 to 25. 000 is particularly preferred.

The component (P1) can be synthesized by a polymerization addition reaction of a polyisocyanate compound (hereinafter, also referred to as “component (I)”) and a polyol (hereinafter, also referred to as “component (O)”). That is, the component (P1) is a reaction product of the component (I) and the component (O). As the component (P1), it is preferable that at least one of the component (I) and the component (O) contains a polymerizable carbon-carbon double bond.

<< Polyisocyanate compound: Component (I) >>
As used herein, the term "polyisocyanate compound" refers to a compound having two or more isocyanate groups (-N = C = O) (polyisocyanate) or a compound having two or more blocked isocyanate groups (blocked poly). Isocyanate). The polyisocyanate is not particularly limited, and those generally used for producing urethane resins can be used without particular limitation.
Blocked polyisocyanate is a compound in which the isocyanate group of polyisocyanate is blocked by a reaction with a blocking agent and is inactivated. The blocked polyisocyanate used as the component (I) is preferably one in which the isocyanate group is blocked by a heat-dissociating blocking agent. Examples of the heat-dissociating blocking agent include blocking agents such as oximes, diketones, phenols, and caprolactams. Blocked polyisocyanates with a heat-dissociable blocking agent have inactive isocyanate groups at room temperature, and when heated, the heat-dissociating blocking agent dissociates and regenerates the isocyanate groups.

Specific examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexanediisocyanate, hydrogenated xylylene diisocyanate, and water. Alicyclic diisocyanates such as supplemented tolylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate; and tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, Aromatic diisocyanates such as trizine diisocyanate, p-phenylenediocyanate, and naphthylene diisocyanate; and these biurets, isocyanurates, and adducts of trimethylolpropane can be mentioned. One type of polyisocyanate may be used alone, or two or more types may be used in combination.

As the polyisocyanate, a commercially available one may be used. Examples of commercially available polyisocyanates include Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, and 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 is the product name, the name manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like. These products may be used alone or in combination of two or more.

Examples of the blocked isocyanate include compounds in which the isocyanate group of the polyisocyanate as described above is protected by a reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermally dissociable blocking agent, that is, a compound that is stable at room temperature but is liberated when heated to a dissociation temperature or higher to generate an isocyanate group, and is known. Anything can be used without particular limitation.
Specific examples of the blocking agent include lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, propiolactam; methylethylketooxime, methylisoamylketooxime, methylisobutylketooxime, formamideoxime, acetamidooxime, etc. Oxime compounds such as acetooxime, diacetylmonooxime, benzophenone oxime, cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, nitrophenol; polycyclic phenol compounds such as 1-naphthol; methyl alcohol, ethyl alcohol, isopropyl alcohol Alcohol compounds such as tert-butyl alcohol, trimethylolpropane, 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; malonic acid alkyl ester, malonic acid dialkyl ester, acet Active oxime compounds such as acetic acid alkyl ester and acetylacetone; and the like. As the blocking agent, one type may be used alone, or two or more types may be used in combination.

The blocked polyisocyanate can be produced by reacting the polyisocyanate with a blocking agent. The reaction between the polyisocyanate and the blocking agent is carried out, for example, in a solvent having no active hydrogen (1.4 dioxane, cellosolve acetate, etc.) under heating at about 50 to 100 ° C., and if necessary, the presence of a blocking catalyst. It is done below. The ratio of the polyisocyanate to the blocking agent is not particularly limited, but the equivalent ratio of the isocyanate group in the polyisocyanate to the blocking agent is preferably 0.95: 1.0 to 1.1: 1.0. , More preferably 1: 1.05 to 1.15. Known blocking catalysts can be used, for example, metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate, potassium methylate; tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium. Hydrooxides; organic weak acid salts such as these acetates, octylates, myristates, benzoates; and alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octyl acid, myristic acid; etc. Be done. As the blocking catalyst, one type may be used alone, or two or more types may be used in combination.

Commercially available block polyisocyanate may be used. Examples of commercially available blocked polyisocyanates include Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate E402-B80B (hereinafter, trade names). , Asahi Kasei Corporation), etc.

As the component (I), blocked polyisocyanate in which the isocyanate group is blocked by a heat dissociative blocking agent is preferable.
As the component (I), one type may be used alone, or two or more types may be used in combination. For example, as the component (I), a mixture of an aliphatic diisocyanate and an aromatic diisocyanate can be used. As the aliphatic diisocyanate, hydrogenated xylene diisocyanate is preferable. As the aromatic diisocyanate, 4,4-diphenylmethane diisocyanate is preferable.

<< polyol: component (O) >>
The polyol (component (O)) is a compound having two or more hydroxy groups (-OH). The polyol is not particularly limited, and those generally used in the production of urethane resin can be used without particular limitation. Examples of the component (O) include a polyol containing a polymerizable carbon-carbon double bond (hereinafter, also referred to as “(O1) component”) and another polyol (hereinafter, also referred to as “(O2) component”). Can be mentioned.

-Polycarbonate containing a polymerizable carbon-carbon double bond ((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 acryloyl group. The polymerizable carbon-carbon double bond contained in the component (O1) may be one or two or more.

Examples of the component (O1) include esters of trivalent or higher valent polyols and methacrylic acid, acrylic acid or derivatives thereof. As the trivalent or higher valence polyol, a trivalent or higher valent small molecule polyol is preferable. Examples of the trihydric or higher low molecular weight polyols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; sorbitol, mannitol and alitol. , Hexal alcohols such as iditol, darsitol, altritor, inositol, dipentaerythritol; heptahydric alcohols such as persetol; and octahydric alcohols such as sucrose; and the like.

Specific examples of the component (O1) include glycerin mono (meth) acrylate, diglycerin tri (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, diglycerin di (meth) acrylate, and 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) Examples include acrylate.
"(Meta) acrylate" is a concept that includes methacrylate and acrylate, and means methacrylate or acrylate.

As the component (O1), one type may be used alone, or two or more types may be used in combination.
Among them, the component (O1) is preferably a diol containing a methacryloyl group or an acryloyl group, and more preferably glycerin mono (meth) acrylate or pentaerythritol di (meth) acrylate.

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

Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, and 1 , 6-Hexanediol, Neopentyl glycol, Alcandiol with 7 to 22 carbon atoms, Diethylene glycol, Triethylene glycol, Dipropylene glycol, 3-Methyl-1,5-Pentanediol, 2-Ethyl-2-butyl-1, 3-Propanediol, alcohol-1,2-diol with 17 to 20 carbon atoms, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol hydride A, 1,4 Dihydric alcohols such as −dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetramethylolmethane (pentaerythritol), Tetrahydric alcohols such as diglycerin; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, aritol, iditol, darsitol, altritor, inositol, dipentaerythritol; Octohydric alcohol; etc.
Among them, the small molecule polyol is preferably a divalent alcohol (diol).

Examples of the high molecular weight polyol include a phenol resin, a resin containing a hydroxystyrene skeleton, a polyester polyol, a polyether polyol, a polyether ester polyol, a polyesteramide polyol, an acrylic polyol, a polycarbonate polyol, a polyhydroxylalkane, a polyurethane polyol, and a vegetable oil type. Examples include polyols. The number average molecular weight of the high molecular weight polyol is preferably 500 to 100,000.

When a small molecule polyol is used as the component (O2), the ratio of the small molecule polyol to the component (O1) (small molecule polyol / component (O1) component (mass ratio)) is preferably 0.01 to 0.1, and is 0. More preferably .03 to 0.08.

[Phenol resin]
The phenol resin may be a novolak type phenol resin or a resol type phenol resin. The novolak-type phenol resin can be obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and aldehydes under an acid catalyst. The resol type phenol resin can be obtained by addition-condensing phenols and aldehydes under an alkaline catalyst.

Examples of the phenols include phenol; cresols such as m-cresol, p-cresol, o-cresol; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and the like. Xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2 Alkylphenols such as −tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol , P-propoxyphenol, alkoxyphenols such as m-propoxyphenol; isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol and the like. Propenylphenols; arylphenols such as phenylphenols; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9, Examples thereof include polyhydroxyphenols such as 9-bis (4-hydroxy-3-methylphenyl) fluorene and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p. -Hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, katsura aldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenyl Benzaldehyde and the like can be mentioned.

The acid catalyst at the time of the addition condensation reaction is not particularly limited, and for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used. The alkali catalyst at the time of the addition condensation reaction is not particularly limited, and sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, sodium carbonate, hexamethylenetetramine and the like are 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 the hydroxystyrene or the hydroxystyrene derivative include the structural unit represented by the following general formula (a10-1).

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｙａ^ｘ１は、単結合又は２価の連結基である。Ｗａ^ｘ１は、（ｎ_ａｘ１＋１）価の芳香族炭化水素基である。ｎ_ａｘ１は、１〜３の整数である。］

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

In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-. Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The alkyl halide group having 1 to 5 carbon atoms of R is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. 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 preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

In the formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.
As the ^{divalent linking group in Ya x1} , for example, a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom are preferable.

A divalent hydrocarbon group that 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.

· · ^{Aliphatic hydrocarbon group in Ya x1} The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic property. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, 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 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Numbers 1 to 4 are more preferable, and carbon numbers 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [−CH ₂ −], an ethylene group [− (CH ₂ ) ₂ −], and a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). Alkylene methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2-, etc.;-} 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 groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH _{2 −.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, the cyclic fat Examples thereof include a group in which the group hydrocarbon group is intervening in the middle of the linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and 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 monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically. Examples thereof 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, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. The methoxy group and the ethoxy group are most preferable.
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 preferable.
Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

Aromatic hydrocarbon group in Ya ^x1 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. 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. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). A group obtained by removing one more atom) and the like. The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon number.

In the aromatic hydrocarbon group, the hydrogen atom contained in 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 with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, halogen atom and alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

-Divalent linking group containing heteroatom:
When Ya ^x1 is a divalent linking group containing a hetero atom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, and -OC. (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H may be substituted with a substituent such as an alkyl group or an acyl group. _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - ^{C (= O) -O -,} - C (= O) -O-Y 21 -, - [Y 21 -C (= O) -O] m "-Y 22 -, - Y 21 -O-C ( = O) ^{-Y 22} - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - group represented by ^{wherein, Y 21} and ^{Y 22} have independently substituent It is also a good divalent hydrocarbon group, where O is an oxygen atom and m "is an integer from 0 to 3. ] Etc. can be mentioned.
The divalent linking group containing the hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). )-, The H may be substituted with a substituent such as an alkyl group or an acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 - _{^{C (= O) -O] m}} "-Y 22 -, - Y 21 -O-C (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -O-Y 22 - in, Y ²¹ and Y ²² are divalent hydrocarbon groups which may independently have a substituent. The divalent hydrocarbon group is mentioned in the description as the divalent linking group. (A divalent hydrocarbon group which may have a substituent) is mentioned.
As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Or 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by group is particularly preferred among them, the formula _{-. (CH 2) a '} -C (= O) -O- (CH 2) b' -. in the group represented by the formula in the formula, a 'is from 1 to 10 Is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b'is an integer of 1 to 10 and of 1 to 8. An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 1 is most preferable.

Ya ^x1 includes a single bond, an ester bond [-C (= O) -O-], an ether bond (-O-), -C (= O) -NH-, and a linear or branched alkylene group. , Or a combination thereof, and a single bond is particularly preferable.

In the formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group having a (n _{ax1 + 1) valence.}
Examples of the aromatic hydrocarbon group in Wa ^x1 include a group obtained by removing _{(n ax1 + 1) hydrogen atoms from the 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 may be a monocyclic type or a polycyclic type. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

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

A specific example of the structural unit represented by the general formula (a10-1) is shown below.
In the formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

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, 3-methyl-1,5-pentanediol, and 1,9-nonane. One or more of diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, etc. Examples thereof include a polycarbonate polyol obtained by reacting the glycol of the above with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgen and the like.

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

［式中、Ｒｐ^１及びＲｐ^２は、それぞれ独立に、２価の炭化水素基である。ｎｐは、２以上の整数である。］

[In the formula, Rp ¹ and Rp ² are independently divalent hydrocarbon groups. np is an integer of 2 or more. ]

In the general formula (PC-1), Rp ¹ and Rp ² are independently divalent hydrocarbon groups. The divalent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of the divalent hydrocarbon group include the same groups as those mentioned ^{in Ya x1 in the general formula (a10-1).} As the ^{divalent hydrocarbon group in Rp 1} and Rp ² , an aliphatic hydrocarbon group is preferable, and a linear or branched alkylene group is more preferable. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. Specific examples of Rp ¹ and Rp ² _{include-(CH 2} ) _6- or-(CH ₂ ) _5- .

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

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

[Other polyols]
Examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebatic acid, dialkyl esters thereof, or mixtures thereof, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, and neo. Glycos such as pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, etc. Examples thereof include polyester polyols obtained by reacting a mixture thereof with polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone). ..

As the polyether polyol, for example, an oxylan compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran is polymerized using a low-volume polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, or glycerin as an initiator. Examples thereof include the obtained polyether polyol.

The polyether ester polyol is obtained by reacting, for example, a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebatic acid or a dialkyl ester thereof or a mixture thereof with the above-mentioned polyether polyol. Examples include polyether ester polyols.

Examples of the polyesteramide polyol include a polyesteramide polyol obtained by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, and hexamethylenediamine as a raw material in the esterification reaction.

Examples of the acrylic polyol include hydroxyethyl acrylate containing one or more hydroxyl groups in one molecule, hydroxyprople acrylate, acrylic hydroxybutyl and the like, or their corresponding methacrylic acid derivatives, and for example, acrylic acid, methacrylic acid or Examples thereof include a polyesteramide polyol obtained by copolymerizing with the ester.

Examples of the polyhydroxyalkane include liquid rubber obtained by copolymerizing butadiene or butadiene with acrylamide or the like.

The polyurethane polyol is a polyol having one or more urethane bonds in one molecule. For example, a polyether polyol having a number average molecular weight of 200 to 20,000, a polyester polyol, a polyether ester polyol, or the like, and a polyisocyanate are used. , Preferably a polyurethane polyol obtained by reacting with an NCO / OH of 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 them, as the vegetable oil-based polyol, castor oil-modified polyol is preferable, and castor oil-modified diol is more preferable.
When a vegetable oil-based polyol is used as the component (O2), the ratio of the vegetable oil-based polyol to the component (O1) (vegetable oil-based polyol / component (O1) component (mass ratio)) is preferably 0.1 to 5, preferably 0.3. ~ 3 is more preferable, and 0.4 to 2.5 is even more preferable.

As the component (O2), one type may be used alone, or two or more types may be used in combination.
Among the above, as the component (O2), a polycarbonate polyol and a small molecule polyol are preferable from the viewpoint of adjusting the viscosity of the adhesive composition and the hardness of the adhesive layer. Further, from the viewpoint of increasing the heat resistance of the adhesive layer, castor oil-modified polyol may be used as the component (O2).

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

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

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

As the component (P1), one type may be used alone, or two or more types may be used in combination.
The content of the component (P1) in the adhesive composition of the present embodiment is not particularly limited as long as it can be applied to a support or the like. The content of the component (P1) in the adhesive composition is preferably 10 to 60% by mass, more preferably 20 to 60% by mass, and 30 to 60% by mass, based on the total amount (100% by mass) of the adhesive composition. Mass% is more preferred.

<Polymerization initiator: component (A)>
The adhesive composition of the present embodiment contains a polymerization initiator (hereinafter, also referred to as component (A)) in addition to the above component (P1). The polymerization initiator is a component having a function of accelerating the polymerization reaction. Examples of the component (A) include a thermal polymerization initiator and a photopolymerization initiator.

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

Examples of the peroxide in the thermal polymerization initiator include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters and the like. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), and 2-chlorobenzoyl peroxide. 3-Chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl -2-Methylpropyl-1-hydroperoxide, pertriphenylacetate-tert-butyl, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, tert-perphenylacetate Examples thereof include butyl, tert-butyl peroxide, and tert-butyl peroxide N- (3-toluyl) carbamate.

Examples of the peroxide include the trade name "Park Mill (registered trademark)", the trade name "Perbutyl (registered trademark)", the trade name "Parloyl (registered trademark)" and the trade name "Perocta" manufactured by Nippon Oil & Fat Co., Ltd. Commercially available products such as "(registered trademark)" can be used.

Examples of the azo-based polymerization initiator in the thermal polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, and 1,1'-azo (methylethyl). Diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyamide , 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2- Methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodi Nitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis- Dimethyl 4-cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1' -Azobisisobutyoxynitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'- Azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobisisobutymen, 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitro Phynoazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2' -Azobisisobutyrate) and the like.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy. -2-Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Molphorinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone 1- [9-ethyl-6- (2-methylbenzoyl)) -9H-carbazole-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4 -Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxy Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4 -Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-Benz anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumempaoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorofe) Nyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer , 2,4,5-Triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethyl Michlers) Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin- t-Butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt- Butyltrichloroacetophenone, pt-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenyl Acrydin, 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) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino) -2-Methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxysti) Lil) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Examples include trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and the like. Be done.

Examples of the photopolymerization initiator include "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade names, all manufactured by BASF) and "NCI-831". Commercially available products such as (trade name, manufactured by ADEKA Corporation) can be used.

As the component (A), one type may be used alone, or two or more types may be used in combination. As the component (A), a thermal polymerization initiator is preferable, and a peroxide is more preferable. The amount of the component (A) used can be adjusted according to the amount of the component (P1) used. The content of the polymerization initiator in the adhesive composition of the present embodiment is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (P1). More preferably.

<Arbitrary ingredient>
The adhesive composition of the present embodiment may contain any component in addition to the above components (P1) and (A) as long as the effects of the present invention are not impaired. The optional component is not particularly limited, and examples thereof include a silane coupling agent, a polymerization inhibitor, a solvent component, a plasticizer, an adhesion aid, a stabilizer, a colorant, and a surfactant.

≪Silane coupling agent: (B) component≫
The adhesive composition of the present embodiment preferably contains a silane coupling agent (hereinafter, also referred to as component (B)) in addition to the above components (P1) and (A). By using the component (B), the adhesion to the substrate can be improved. Further, in a resin substrate such as a molded substrate, voids are likely to occur at a high temperature. By using the component (B), the generation of voids can be suppressed even in the resin substrate.
The silane coupling agent is a silane compound having two types of functional groups having different reactivity. The two types of functional groups are preferably hydrolyzable groups and other functional groups. The "hydrolyzable group" refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like. The alkoxy group and the acyloxy group preferably have 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. Among them, as the hydrolyzable group, an alkoxy group is preferable, and an ethoxy group or a methoxy group is more preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group, and more preferably a compound having an ethoxysilyl group or a methoxysilyl group.

The functional group other than the hydrolyzable group is not particularly limited, and examples thereof include an epoxy group, an amino group, an isocyanate group, a vinyl group, a (meth) acryloyl group, a mercapto group, a ureido group, and a styryl group. Not limited to these. When used for adhering an inorganic substrate such as a silicon substrate, an epoxy group, an amino group, or an isocyanate group is preferable. When used for adhering a resin substrate such as a molded substrate, an epoxy group is preferable. "(Meta) acryloyl group" is a concept including a methacryloyl group and an acryloyl group, and means a methacryloyl group or an acryloyl group.

Examples of the component (B) include a compound represented by the following general formula (b1) (hereinafter, also referred to as “compound (B1))).
Y-L-SiR _3-n X _n ... (b1)
[In the formula, X represents a hydrolyzable group; Y represents a functional group other than the hydrolyzable group; L represents a divalent linking group; R represents an alkyl group; n is an integer of 1-3. Represents. ]

X in the general formula (b1) represents a hydrolyzable group directly linked to a silicon atom. X is similar to the hydrolyzable group described above.
Y in the general formula (b1) represents a functional group other than the hydrolyzable group. Y is the same as the functional group described above.
L in the general formula (b1) represents a divalent linking group. Examples of the divalent linking group in L include those similar to those mentioned in ^{Ya x1 in the above formula (a10-1).} The divalent linking group in L is preferably an aliphatic hydrocarbon group which may have a heteroatom, and more preferably an alkylene group which may have a heteroatom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like. As for L, some of the methylene groups are -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-, -C (= O). ) -NH-, -NH-, -NH-C (= NH)-(H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S (= O). _An alkylene group, which may be substituted with 2- or −S (= O) _{2-O−, is preferred.} As L, an alkylene group in which a part of the methylene group may be substituted with -O- or -NH- is more preferable. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms.
R in the general formula (b1) represents an alkyl group. The alkyl group of R preferably has 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms, and more preferably a methyl group.
N in the general formula (b1) represents an integer of 1 to 3. n is preferably 2 or 3, more preferably 3.

Examples of the compound (B1) in which Y is an epoxy group include 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 2 (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3 − Glycydoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, and the like, but are not limited thereto.

Examples of the compound (B1) in which Y is an amino group include N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3 −Aminopropyldimethoxysilane, 3-aminopropyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, Examples thereof include, but are not limited to, N-phenyl-3-aminopropyltrimethoxysilane.

Examples of the compound (B1) in which Y is an isocyanate group include, but are not limited to, 3-isocyanatepropyltriethoxysilane and the like.

Examples of the compound (B1) in which Y is a vinylto group include, but are not limited to, vinyltrimethoxysilane and vinyltriethoxysilane.

Examples of the compound (B1) in which Y is a (meth) acryloyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxy. Examples thereof include, but are not limited to, propyltriethoxysilane and 3-acryloxypropyltrimethoxysilane.

Examples of the compound (B1) in which Y is a mercapto group include, but are not limited to, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Examples of the compound (B1) in which Y is a ureido group include, but are not limited to, 3-ureidopropyltrialkoxysilane.

Examples of the compound (B1) in which Y is a styryl group include, but are not limited to, p-styryltrimethoxysilane.

Commercially available products of compound (B1) include, for example, KBM-303, KBM-402, KBM-403, KBE402, KBE-403, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-802, KBM-803, KBE-585A, KBM- 1403 (all manufactured by Shin-Etsu Chemical Co., Ltd.); Z-6883, OFS-6032, Z-6269, OFS-6032, OFS-6032, Z-6119, Z-6120, Z-6675, OFS-6040, Z-6044, Examples thereof include Z-6043, Z-6075, Z-6300, Z-6019, Z-6825, OFS-6030, Z-6033, and Z-6062 (all manufactured by Dow Toray Co., Ltd.).

The component (B) may be a polymer-type silane coupling agent. Examples of the polymer type silane coupling agent include a polysiloxane type silane coupling agent and an organic polymer type silane coupling agent.

The polysiloxane type silane coupling agent has a hydrolyzable group and a functional group other than the hydrolyzable group bonded to a polymer having a polysiloxane skeleton (a polymer composed of repeating units of −Si—O—) in the main chain. It is a silane coupling agent. The polysiloxane type silane coupling agent is a hydrolyzed condensate of the silane coupling agent of compound (B1).
Examples of commercially available polysiloxane-type silane coupling agents include KR-517, KR-516, KR-513, X-41-1805, and X41-1810 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The organic polymer type silane coupling agent is a silane coupling agent in which a hydrolyzable group and a functional group other than the hydrolyzable group are bonded to an organic polymer having an organic structure as a main chain. The organic polymer is not particularly limited, and any organic polymer can be used. The organic polymer type silane coupling agent preferably has an ethoxy group or a methoxy group as a hydrolyzable group. When used for a silicon substrate, those having an epoxy group, an amino group, or an isocyanate group as a functional group are preferable. When used for a resin substrate, those having an epoxy group as a functional group are preferable. As the functional group equivalent (the number of functional groups per silicon atom), for example, 1 to 10 is preferable, 1 to 5 is more preferable, and 2 or 3 is further preferable.
Examples of commercially available organic polymer type silane coupling agents include X-12-972F, X-12-981S, X-12-984S, X-12-1048, X-12-1050, and X-12-1154. , X-12-1242, X-12-1159L (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Preferred examples of the component (B) include a compound (B1) having an epoxy group, an amino group, or an isocyanate group, or an organic polymer type silane coupling agent having an epoxy group, an amino group, or an isocyanate group. When used for adhering a resin substrate, a compound having an epoxy group (B1) or an organic polymer type silane coupling agent having an epoxy group is particularly preferable.

As the component (B), one type may be used alone, or two or more types may be used in combination. As the component (B), an appropriate one can be selected according to the type of the substrate. For example, when the object to be bonded is a silicon substrate, a silane coupling agent having an epoxy group, an amino group, or an isocyanate group can be used. For example, when the object to be bonded is a resin substrate, a silane coupling agent having an epoxy group can be used.

When the adhesive composition of the present embodiment contains the component (B), the content of the component (B) is, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (P1). It is more preferably 1 to 10 parts by mass, further preferably 1 to 5 parts by mass, and particularly preferably 3 to 5 parts by mass.

≪Polymerization inhibitor≫
A polymerization inhibitor refers to a component having a function of preventing a radical polymerization reaction due to heat or light. Polymerization inhibitors are highly reactive with radicals.

As the polymerization inhibitor, those having a phenol skeleton are preferable. For example, a hindered phenolic antioxidant can be used as the polymerization inhibitor, such as pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, and amyloxyhydroquinone. , N-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6-dimethylphenol) ), 4,4'-[1- [4- (1- (4-Hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4', 4 "-ethylidentris (2-methylphenol) , 4,4', 4 "-Etilidentrisphenol, 1,1,3-Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl-4- Methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl- 6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octyl-3- (3,3) 5-Di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, manufactured by BASF), Tris (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like can be mentioned.

As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination.
The content of the polymerization inhibitor may be appropriately determined according to the type of resin component, the use of the adhesive composition, and the environment in which it is used.

≪Surfactant≫
Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like.

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

Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, and aralkyl-modified silicone-based surfactants. , And reactive silicone-based surfactants and the like. As the silicone-based surfactant, a commercially available one can be used. Specific examples of commercially available silicone-based surfactants include, for example, Painted M (manufactured by Toray Dow Corning), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyester modification). Examples thereof include silicone-based surfactants (manufactured by Clariant) and BYK-310 (polyester-modified silicone-based surfactants manufactured by Big Chemie).

As the surfactant, one type may be used alone, or two or more types may be used in combination. As the surfactant, a silicone-based surfactant is preferable, and a polyester-modified silicone-based surfactant is more preferable. When a surfactant is used, the content of the surfactant in the adhesive composition of the present embodiment is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (P1), and 0. It is more preferably 05 to 0.5 parts by mass.

≪Solvent component≫
The adhesive composition of the present embodiment can be prepared by dissolving and mixing the components (P1) and (A) and, if necessary, an optional component in a solvent component. 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-based solvents, and other solvents other than the above-mentioned solvents. Hereinafter, the hydrocarbon solvent and the petroleum solvent are collectively referred to as "(S1) component". A solvent component other than the component (S1) is also referred to as a “component (S2)”.

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; and branched hydrocarbons such as isooctane, isononan, and isododecane; p. -Menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpinene, 1,8-terpinene, bornan, norbornan, pinan, tsujan, karan, longihoren, α-terpinene, β-terpinene, γ-terpinene, Alicyclic hydrocarbons such as α-pinene, β-pinene, α-tujon, β-tujon, cyclohexane, cycloheptane, cyclooctane; toluene, xylene, inden, pentalene, indan, tetrahydroinden, naphthalene, tetrahydronaphthalene (tetraline) ), Aromatic hydrocarbons such as decahydronaphthalene (decalin).

The petroleum-based solvent is a solvent refined from heavy oil, and examples thereof include white kerosene, paraffin-based solvent, and isoparaffin-based solvent.

Examples of the component (S2) include a terpene solvent having an oxygen atom, a carbonyl group, an acetoxy group or the like as a polar group. , Β-terpineol, γ-terpineol, terpine-1-ol, terpine-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carboxylic, yonon, tsuyon, camphor, etc. Can be mentioned.

In addition, as the component (S2), lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol. , Polyvalent alcohols such as propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyvalent alcohols or the esters. Derivatives of polyhydric alcohols such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monoalkyl ethers such as monobutyl ethers, and compounds having ether bonds such as monophenyl ethers (among these, propylene glycol). Monomethyl ether acetate (PGMEA), 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, Esters such as methyl methoxypropionate and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol and butylphenyl ether can also be mentioned.

As the solvent component, one type may be used alone, or two or more types may be used in combination. The solvent component is preferably one that is inert to the component (P1). Preferred solvent components include, for example, ester-based solvents, ketone-based solvents, aromatic hydrocarbon-based solvents, PGMEA, PGME, and mixed solvents thereof.

The content of the solvent component in the adhesive composition of the present 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% by mass with respect to the total amount (100% by mass) of the adhesive composition, for example. That is, the adhesive composition of the present embodiment preferably has a solid content (total amount of compounding components excluding the solvent component) concentration in the range of 10 to 80% by mass. When the content of the solvent component is within the above-mentioned preferable range, the viscosity can be easily adjusted.

The polymerization initiator can be blended by a known method immediately before using the adhesive composition. The polymerization initiator or polymerization inhibitor may be blended in the form of a solution previously dissolved in the above component (S2). The amount of the component (S2) used may be appropriately adjusted according to the type of the polymerization initiator or the polymerization inhibitor. For example, 1 to 50 parts by mass is preferable with respect to 100 parts by mass of the component (S1). ~ 30 parts by mass is more preferable. When the amount of the component (S2) used is within the above-mentioned preferable range, the polymerization initiator or the polymerization inhibitor can be sufficiently dissolved.

According to the adhesive composition of the present embodiment, when the semiconductor substrate or electronic device and the support are temporarily bonded, the component (P1) is polymerized and crosslinked by a polymerizable carbon-carbon double bond. .. As a result, the adhesive composition layer is cured to form an adhesive layer, and the semiconductor substrate or electronic device and the support are temporarily bonded. Since the adhesive layer is cured by the crosslinked structure, it has high heat resistance, and the elastic modulus does not decrease even at a high temperature (for example, 200 ° C. or higher). Therefore, even when high-temperature processing is performed when processing a semiconductor substrate or an electronic device, problems such as misalignment and subduction are unlikely to occur.

On the other hand, in the adhesive layer, the urethane bond in the component (P1) can be decomposed by an acid or an alkali. Therefore, when the processing of the semiconductor substrate or the electronic device on the support is completed and the semiconductor substrate or the electronic device and the support are separated, an acid or an alkali is allowed to act on the adhesive layer. As a result, the urethane bond is decomposed and the component (P1) is decomposed, so that the adhesive layer can be removed. As a result, the semiconductor substrate or electronic device and the support can be easily separated. Further, the residue of the adhesive layer adhering to the semiconductor substrate or the electronic device can be easily removed by an acid or an alkali.

(Laminated body)
The laminate according to the second aspect of the present invention is a laminate in which a support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, and the adhesive layer has an adhesive composition according to the first aspect. It is characterized by being a cured product of an object.

FIG. 1 shows an embodiment of the laminated body according to the second aspect.
The laminate 100 shown in FIG. 1 includes a support 12 in which a support substrate 1 and a separation layer 2 are laminated, an adhesive layer 3, and a semiconductor substrate 4. In the laminated body 100, the support 12, the adhesive layer 3, and the semiconductor substrate 4 are laminated in this order.
In the example of FIG. 1, the support 12 is composed of the support base 1 and the separation layer 2, but the support is not limited to this, and the support may be formed only from the support base.

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

FIG. 3 shows yet another embodiment of the laminate according to the second aspect.
The laminated body 300 shown in FIG. 3 has the same configuration as the laminated body 100 except that the electronic device is composed of the wiring layer 6.

FIG. 4 shows yet another embodiment of the laminate according to the second aspect.
The laminate 400 shown in FIG. 4 has the same configuration as the laminate 100 except that the electronic device 645 composed of the wiring layer 6, the semiconductor substrate 4, and the encapsulant layer 5 is laminated on the adhesive layer 3. ..

<Support>
The support is a member that supports a semiconductor substrate or an electronic device. In the examples of FIGS. 1 to 4, the support 12 includes a support base 1 and a separation layer 2 provided on the support base 1. In the laminated body of the present embodiment, the support may or may not have the separation layer 2. When the support does not have the separation layer 2, the support base 1 becomes the support.

≪Supporting base≫
The support substrate is a member that has a property of transmitting light and supports a semiconductor substrate or an electronic component. When the separation layer is provided as shown in FIGS. 1 to 4, the support substrate is attached to the semiconductor substrate or the electronic device via the separation layer and the adhesive layer. When the separation layer is not provided, the support substrate is bonded to the semiconductor substrate or the electronic device via the adhesive layer. Therefore, it is preferable that the support substrate has the strength necessary to prevent the semiconductor substrate from being damaged or deformed when the device is thinned, the semiconductor substrate is transported, or the semiconductor substrate is mounted on the semiconductor substrate. When the support has a separation layer, the support substrate preferably transmits light having a wavelength capable of altering the separation layer.
As the material of the support substrate, for example, glass, silicon, an acrylic resin or the like is used. Examples of the shape of the support substrate include, but are not limited to, a rectangle, a circle, and the like. As the support substrate, a circular support substrate with a larger size or a large panel having a quadrangular shape in a plan view can be used in order to further increase the density and improve the production efficiency.

≪Separation layer≫
The separation layer is a layer adjacent to the adhesive layer, which is altered by irradiation with light and enables the support substrate to be separated from the semiconductor substrate or the electronic device fixed to the support via the adhesive layer.
This separation layer can be formed by using the composition for forming a separation layer described later, for example, by firing a component contained in the composition for forming a separation layer, or by a chemical vapor deposition (CVD) method. It is formed. This separation layer is suitably denatured by absorbing the light transmitted through the support substrate and irradiated.
The separation layer is preferably formed only from a material that absorbs light, but is a layer containing a material that does not have a structure that absorbs light within a range that does not impair the essential properties of the present invention. There may be.

The thickness of the separation layer is, for example, preferably in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. When the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, the separation layer can be subjected to desired alteration by short-time light irradiation and low-energy light irradiation. Further, the thickness of the separation layer is particularly preferably in the range of 1 μm or less from the viewpoint of productivity.

The surface of the separation layer on the side in contact with the adhesive layer is preferably flat (no unevenness is formed), whereby the adhesive layer can be easily formed, and the semiconductor substrate or electronic device and the support substrate can be easily formed. And can be easily attached evenly.

-Composition for forming a separation layer The composition for forming a separation layer, which is a material for forming a separation layer, includes, for example, fluorocarbon, a polymer having a repeating unit including a structure having light absorption, an inorganic substance, and infrared rays. Examples thereof include compounds having an absorbable structure, infrared absorbers, reactive polysilsesquioxane, and those containing a resin component having a phenol skeleton.
Further, the composition for forming a separation layer improves the separability of a filler, a plasticizer, a thermoacid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a support substrate as optional components. It may contain a possible component or the like.

The fluorocarbon separation layer may contain fluorocarbon. The separation layer composed of fluorocarbons is adapted to change in quality by absorbing light, and as a result, loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is destroyed, and the support and the semiconductor substrate or the electronic device can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed by a plasma CVD method.
Fluorocarbons absorb light with wavelengths in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the fluorocarbon used for the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or more.

The light irradiated to the separation layer, in accordance with the fluorocarbon wavelength absorbable, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, a solid laser such as a fiber laser, a liquid laser dye laser, , CO ₂ laser, excimer laser, Ar laser, gas laser such as He-Ne laser, laser light such as semiconductor laser, free electron laser, or non-laser light may be appropriately used. As the wavelength capable of altering the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

The polymer separation layer having a repeating unit containing a structure having a light absorption property may contain a polymer having a repeating unit containing a structure having a light absorption property. The polymer is altered by being irradiated with light.
Examples of the structure having light absorption include an atomic group containing a conjugated π-electron system composed of a substituted or unsubstituted benzene ring, a condensed ring or a heterocycle. More specifically, the structure having light absorption is a cardo structure, or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), or a diphenyl present in the side chain of the polymer. The structure or the diphenylamine structure can be mentioned.
The above-mentioned structure having light absorption ability can absorb light having a wavelength in a desired range depending on the type thereof. For example, the wavelength of light that can be absorbed by the structure having light absorption is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

The light that can be absorbed by the above-mentioned light-absorbing structure is, for example, a high-pressure mercury lamp (wavelength 254 nm or more and 436 nm or less), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ Light emitted from an excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), XeF laser (wavelength 351 nm) or solid UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line. (Wavelength 365 nm) and the like.

-The inorganic substance separation layer may be made of an inorganic substance. The inorganic substance may be any one that is altered by absorbing light, and for example, one or more kinds selected from the group consisting of metals, metal compounds and carbon are preferably mentioned. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.
Such inorganic, gold, silver, copper, iron, nickel, aluminum, titanium, _{chromium, SiO 2, SiN, Si 3} N 4, TiN, and one or more selected from the group consisting of carbon and the like.
Note that carbon is a concept that may include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.
The above-mentioned inorganic substances absorb light having a wavelength in a unique range depending on the type.

The light irradiating the separation layer made of an inorganic substance includes, for example, _{a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO 4} laser, an LD laser, and a fiber laser, and a dye laser, depending on the wavelength that the inorganic substance can absorb. Liquid lasers such as, CO ₂ lasers, excimer lasers, Ar lasers, gas lasers such as He-Ne lasers, laser beams such as semiconductor lasers and free electron lasers, or non-laser lasers may be appropriately used.
The separation layer made of an inorganic substance can be formed on the support substrate by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like.

The compound separation layer having an infrared absorbing structure may contain a compound having an infrared absorbing structure. This compound having an infrared absorbing structure is altered by absorbing infrared rays.
Examples of the structure having infrared absorption or the compound having this structure include alkane, alkene (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumlen, cyclic), and alkyne (1). Substitution, di-substituted), monocyclic aromatics (benzene, mono-substituted, di-substituted, tri-substituted), alcohols or phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary, saturated tertiary) Class, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxylan ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 -Diketone enol, o-hydroxyarylketone, dialkylaldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β) -, Γ-, δ-), Aliphatic acid compounds, Aromatic acid compounds, Acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, Primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary Secondary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanic acid esters, thiocyanic acid esters, aliphatic isothiocyanate esters, aromatic isothiocyanate esters, aliphatic nitro compounds, Aromatic nitro compounds, nitroamines, nitrosoamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatics, monomers, dimers), sulfur compounds such as mercaptans or thiophenols or thiolic acids, thiocarbonyl groups, Sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² Bonds (A ² is H, C or O) or Ti-O bonds can be mentioned.

Examples of the structure containing a carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF _{2- , -CF 3} , -CH = CF ₂ , -CF = CF ₂ , and fluorine. Aryl carbonate, aryl chloride and the like can be mentioned.

As a structure containing ^{Si-A 1} bond described above, for _{example, SiH, SiH 2, SiH 3} , Si-CH 3, Si-CH 2 -, Si-C 6 H 5, SiO- aliphatic, Si-OCH ₃ , Si-OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ or SiF _{3 and the} like. As the structure containing the Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton or a silsesquioxane skeleton.

Examples of the ^{structure containing the PA 2} bond include PH, PH ₂ , P-CH ₃ , P-CH _2- , P-C ₆ H ₅ , A ³ ₃ -PO (A ³ is a fat). Group group or aromatic group), (A ⁴ O) _3- P-O (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , P-O-P , P-OH or O = P-OH and the like.

Examples of the above-mentioned compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate and the like. Alkoxytitanium; (ii) di-i-propoxybis (acetylacetonato) titanium or chelated titanium such as propanedioxytitanium bis (ethylacetacetate); (iii) i-C ₃ H ₇ O-[-Ti ( O-i-C ₃ H ₇ ) _2- O-] _n- i-C ₃ H ₇ or n-C ₄ H ₉ O- [-Ti (On-C ₄ H ₉ ) _2- O-] _n titanium polymers such _{-n-C 4 H 9; (} iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisostearate or (2-n-butoxycarbonyl benzoyloxy) Achilled titanium such as tributoxytitanium; and water-soluble titanium compounds such as (v) di-n-butoxy-bis (triethanolaminato) titanium can be mentioned.
Among these, compounds containing a Ti—O bond include di-n-butoxy-bis (triethanolamineto) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH)). ₂ ] ₂ ) is preferable.

The above-mentioned infrared-absorbing structure can absorb infrared rays having a wavelength in a desired range, depending on the type of selection. Specifically, the wavelength of infrared rays that can be absorbed by the above-mentioned infrared-absorbing structure is, for example, in the range of 1 to 20 μm, and more preferably in the range of 2 to 15 μm.
Further, when the structure is a Si—O bond, a Si—C bond or a Ti—O bond, the range is preferably in the range of 9 to 11 μm.

Those skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each of the above structures. For example, as an absorption band in each structure, Non-Patent Documents: SILVERSTEIN, BASSLER, MORRRILL, "Identification method by spectrum of organic compounds (5th edition) -Combination of MS, IR, NMR, UV-" (published in 1992) References can be made to the description on pages 146 to 151.

As a compound having an infrared absorbing structure used for forming a separation layer, among the compounds having the above-mentioned structure, the compound can be dissolved in a solvent for coating and solidified to form a solid layer. Is not particularly limited as long as it can form. However, in order to effectively alter the compound in the separation layer and facilitate the separation between the support substrate and the substrate, the absorption of infrared rays in the separation layer is large, that is, the infrared rays when the separation layer is irradiated with infrared rays. It is preferable that the transmittance is low. Specifically, the infrared transmittance in the separation layer is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

The infrared absorbing substance separation layer may contain an infrared absorbing substance. The infrared absorbing substance may be any substance that is altered by absorbing light, and for example, carbon black, iron particles, or aluminum particles can be preferably used.
Infrared absorbers absorb light with wavelengths in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the infrared absorbing substance used for the separation layer, the infrared absorbing substance can be suitably altered.

The reactive polysilsesquioxane separation layer can be formed by polymerizing the reactive polysilsesquioxane. The separation layer formed thereby has high chemical resistance and high heat resistance.

"Reactive polysilsesquioxane" refers to polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. .. By condensing the silanol group or a functional group capable of forming a silanol group, they can be polymerized with each other. Further, if the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, it can form a silsesquioxane skeleton such as a random structure, a cage-shaped structure, or a ladder structure. Reactive polysilsesquioxane provided can be adopted.

The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol%, more preferably 80 to 99 mol%.
If the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably altered by irradiating with infrared rays (preferably far infrared rays, more preferably light having a wavelength of 9 to 11 μm). A possible separation layer can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, more preferably 1,000 to 10,000.
If the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably dissolved in a solvent and can be suitably applied on a support plate.

Examples of commercially available products that can be used as the reactive polysilsesquioxane include SR-13, SR-21, SR-23, and SR-33 (trade name) manufactured by Konishi Chemical Industry Co., Ltd.

-Resin component having a phenol skeleton The separation layer may contain a resin component having a phenol skeleton. By having a phenol skeleton, it is easily altered (oxidized, etc.) by heating or the like, and photoreactivity is enhanced.
As used herein, "having a phenol skeleton" means that it contains a hydroxybenzene structure.
The resin component having a phenol skeleton has a film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30,000, further preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is not more than the upper limit of the above-mentioned preferable range, the solubility of the composition for forming a separation layer in a solvent is enhanced.
As the molecular weight of the resin component, the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography) is used.

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

<Adhesive layer>
The adhesive layer is provided to temporarily bond the semiconductor substrate or the electronic device to the support. The adhesive layer is a cured product of the adhesive composition according to the first embodiment. More specifically, the adhesive layer is formed by polymerizing and cross-linking the component (P1) in the adhesive composition according to the first embodiment by a polymerizable carbon-carbon double bond. The polymerization reaction of the component (P1) can be carried out by heating the adhesive composition. The thickness of the adhesive layer is preferably in the range of, for example, 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.

As described above, the adhesive layer is a cured product of the adhesive composition, and the material (cured product) constituting the adhesive layer preferably satisfies the following characteristics.
That is, when measuring the complex elastic modulus of the cured product under the following conditions, is preferably, 5.0 × ¹⁰ 6 Pa or more that a complex elastic modulus at 200 ° C. is 1.0 × ¹⁰ 6 Pa or more it is more preferred, further preferably 1.0 × ¹⁰ 7 Pa or higher. The upper limit of the complex elastic modulus at 200 ° C. is, for example, 1.0 × 10 ¹⁰ Pa or less.
Also, when measuring the complex elastic modulus of the cured product under the following conditions, is preferably, 1.0 × ¹⁰ 7 Pa or higher that the complex elastic modulus is 5.0 × ¹⁰ 6 Pa or more at 250 ° C. Is more preferable. 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 cured product can be measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition is applied onto a PET film with a mold release agent, and heated in an oven under a nitrogen atmosphere at 180 ° C. for 1 hour to form a test piece having a thickness of 50 μm, and then PET. The test piece (size 5 mm × 40 mm, thickness 50 μm) peeled off from the film can be measured using the above-mentioned measuring device. As the measurement conditions, a condition may be adopted in which the temperature is raised from a starting temperature of 50 ° C. to 300 ° C. at a heating rate of 5 ° C./min under a tensile condition having a frequency of 1 Hz.

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

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

≪Electronic device≫
The electronic device is not particularly limited, and examples thereof are the same as those exemplified in the above "(adhesive composition)". The electronic device is preferably a composite of a member made of a 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 can further include a semiconductor substrate.
In the laminate 200 shown in FIG. 2, the electronic device 456 is composed of a semiconductor substrate 4, a sealing material layer 5, and a 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 laminate 400 shown in FIG. 4, the electronic device 645 is composed of a wiring layer 6, a semiconductor substrate 4, and a sealing material layer 5.

[Encapsulant layer]
The encapsulant layer is provided for encapsulating the semiconductor substrate, and is formed by using the encapsulant. As the sealing material, a member capable of insulating or sealing a member made of metal or a semiconductor is used.
As the sealing material, for example, a resin composition can be used. The encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3. The resin used for the encapsulant is not particularly limited as long as it can encapsulate and / or insulate a metal or semiconductor, and examples thereof include epoxy resins and silicone resins.
The sealing material may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles and the like.

≪Wiring layer≫
The wiring layer is also called an RDL (Redistribution Layer), and is a thin film wiring body constituting a wiring connected to a substrate, and may have a single layer or a plurality of layers structure. The wiring layer is composed of conductors (for example, metals such as aluminum, copper, titanium, nickel, gold and silver, and silver-tin) between dielectrics (silicon oxide (SiO _{x), photosensitive resins such as photosensitive epoxy).} The wiring may be formed of an alloy such as an alloy), but the wiring is not limited to this.

In the laminated body of FIGS. 1 to 4, the support substrate 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and another layer is further formed between the support substrate 1 and the separation layer 2. It may have been done. In this case, the other layer may be composed of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts preferable properties and the like to the laminated bodies 100 to 400 without hindering the incident of light on the separation layer 2. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 2. Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from the materials transmitting light having a wavelength capable of altering the material constituting the separation layer 2.

(Manufacturing method of laminated body (1))
The method for producing a laminate according to a third aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, and the first aspect is applied to the support or the semiconductor substrate. A step of applying the adhesive composition according to the above to form an adhesive composition layer (hereinafter, also referred to as an "adhesive composition layer forming step"), and the semiconductor substrate on the support, the adhesive. A step of mounting via the composition layer (hereinafter, also referred to as a "semiconductor substrate mounting step") and a step of curing the adhesive composition layer by a polymerization reaction of the urethane resin to form the adhesive layer. (Hereinafter, also referred to as "adhesive layer forming step").

5 to 6 are schematic process diagrams for explaining one embodiment of the method for manufacturing a laminated body according to the present embodiment.
5 (a) to 5 (c) are views for explaining the manufacturing process of the laminate 100'in which the support 12, the adhesive composition layer 3', and the semiconductor substrate 4 are laminated in this order. FIG. 5A is a diagram showing the support 12. The support 12 is composed of a support base 1 and a separation layer 2. FIG. 5B is a diagram illustrating an adhesive composition layer forming step. FIG. 5C is a diagram illustrating a semiconductor substrate mounting process.
FIG. 6 is a diagram illustrating an adhesive layer forming step. The adhesive composition layer 3'in the laminated body 100'is thermoset to form the adhesive layer 3 to obtain the laminated body 100.

[Adhesive composition layer forming step]
The method for producing a laminate according to the present embodiment includes an adhesive composition layer forming step. The adhesive composition layer forming step is a step of applying the adhesive composition to the support or the semiconductor substrate to form the adhesive composition layer. When the support has a separation layer, the adhesive composition layer is formed on the surface of the support on the side having the separation layer.
In FIG. 5B, the adhesive composition layer 3'is formed on the surface of the support 12 on the separation layer 2 side using the adhesive composition.

The method for forming the adhesive composition layer 3'on the support 12 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blades, spray coating, and slit coating.
The adhesive composition layer may be formed on the semiconductor substrate 4 in the same manner.

After forming the adhesive composition layer, a baking treatment may be performed. The bake temperature condition is 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 the component (P1) contained in the adhesive composition, and examples thereof include 1 to 10 minutes under a temperature condition of 70 to 100 ° C.

[Semiconductor substrate mounting process]
The method for manufacturing a laminate according to the present embodiment includes a semiconductor substrate mounting step. 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. 5C, the semiconductor substrate 4 is placed on the support 12 via the adhesive composition layer 3'formed on the support 12.

The method of mounting the semiconductor substrate 4 on the support 12 via the adhesive composition layer 3'is not particularly limited, and a method generally used as a method of arranging the semiconductor substrate at a predetermined position is adopted. be able to.

[Adhesive layer forming process]
The method for producing a laminate according to the present embodiment includes an adhesive layer forming step. The adhesive layer forming step is a step of curing the adhesive composition layer by the polymerization reaction of the urethane resin ((P1) component) in the adhesive composition layer to form the adhesive layer. Thereby, the laminated body 100 can be obtained.
In FIG. 6, the adhesive layer 3 is formed by curing the adhesive composition layer 3'.

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

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

By this step, the component (P1) in the adhesive composition layer 3'is crosslinked and cured to form the adhesive layer 3 which is a cured product of the adhesive composition layer 3'. As a result, the support 12 and the semiconductor substrate 4 are temporarily bonded to each other. As a result, the laminated body 100 can be obtained.

[Arbitrary process]
The method for producing a laminate according to the present embodiment may include other steps in addition to the above steps. Other steps include, for example, a separation layer forming step, and various mechanical or chemical treatments (thinning treatments such as gliding and chemical mechanical polishing (CMP), chemical vapor deposition (CVD), and physical vapor deposition (Chemical vapor deposition). Treatment under high temperature and vacuum such as PVD), treatment using chemicals such as organic solvent, acidic treatment liquid and basic treatment liquid, plating treatment, irradiation with active light, heating / cooling treatment, etc.) can be mentioned.

-Separation layer forming step When the support includes a separating layer, the method for producing a laminate according to the present embodiment may include a separating layer forming step. The separation layer forming step is a step of forming a separation layer on one side of the support substrate using the composition for forming the separation layer.
In FIG. 5A, a separation layer 2 is formed on the support substrate 1 by using a composition for forming a separation layer (containing fluorocarbon) (that is, a support substrate with a separation layer is produced). There is).

The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blades, spray coating, slit coating, and chemical vapor deposition (CVD).
For example, in the separation layer forming step, the solvent component is removed from the coating layer of the separation layer forming composition coated on the support substrate 1 under a heating environment or a reduced pressure environment to form a film, or the support substrate 1 is formed. The support 12 can be obtained by forming a film on the film by a vapor deposition method.

(Manufacturing method of laminated body (2))
In the method for manufacturing a laminate according to a fourth aspect of the present invention, after obtaining the laminate by the method for producing a laminate according to the third aspect, a member made of a metal or a semiconductor and the member are sealed. It is characterized by further having an electronic device forming step of forming an electronic device, which is a composite of a resin for stopping or insulating.

The laminate obtained by the method for producing a laminate of the present embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order. The laminated body can be obtained by performing an electronic device forming step on the laminated body obtained by the method for producing a laminated body according to the third aspect.

[Electronic device formation process]
The method for producing a laminate according to the present embodiment includes an electronic device forming step. The electronic device forming step is a step of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.
The electronic device forming step can include any 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 the sealing process The sealing process is a step of sealing the substrate fixed on the support with a sealing material.
In FIG. 7A, a laminate 110 is obtained in which the entire semiconductor substrate 4 temporarily bonded to the support 12 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 onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high viscosity state, and is compression-molded. As a result, a laminated body 110 in which the sealing material layer 5 is provided on the adhesive layer 3 is produced.
At that 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 encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3.

-Grinding step The grinding step is a step of grinding the sealing material portion (sealing material layer 5) of the sealing body after the sealing step so that a part of the semiconductor substrate is exposed.
As shown in FIG. 7B, for example, the encapsulant portion is ground by grinding the encapsulant layer 5 to a thickness substantially equal to that of the semiconductor substrate 4.

-About the wiring layer forming step The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor substrate after the grinding step.
In FIG. 7C, 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 laminate 120, the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 constitute an electronic device 456.

Examples of the method for forming the wiring layer 6 include the following methods.
_{First, a dielectric layer such as silicon oxide (SiO x} ) or a photosensitive resin is formed on the sealing material layer 5. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying the photosensitive resin on the sealing material layer 5 by a method such as spin coating, dipping, roller blade, spray coating, slit coating or the like. ..

Subsequently, wiring is formed on the dielectric layer with a conductor such as metal. As a method for forming the wiring, for example, a known semiconductor process method such as a lithography process such as photolithography (resist lithography) or an etching process can be used. Examples of such a lithography process include a lithography process using a positive resist material and a lithography process using a negative resist material.

In the method for manufacturing a laminated body according to the present embodiment, bumps can be further formed on the wiring layer 6 or elements can be mounted. The element can be mounted on the wiring layer 6 by using, for example, a chip mounter or the like.

(Manufacturing method of laminated body (3))
The method for producing a laminated body according to a fifth aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer, and an electronic device are laminated in this order, and the first aspect is described on the support. A step of applying such an adhesive composition to form a layer of the adhesive composition (adhesive composition layer forming step), a member composed of a metal or a semiconductor, and a resin for sealing or insulating the member. The adhesive composition layer is cured by an electronic device forming step (electronic device forming step) in which an electronic device, which is a composite of the above, is formed on the adhesive composition layer, and a polymerization reaction of the urethane resin. It is characterized by having a step of forming an adhesive layer (adhesive layer forming step).

The laminate obtained by the method for producing a laminate of the present embodiment is a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, as in the production method according to the fourth aspect.

In the production method of the present embodiment, the adhesive composition layer forming step can be performed in the same manner as in the production method of the laminate according to the third aspect.

In the manufacturing method of the present embodiment, an electronic device forming step is performed after the adhesive composition layer forming step. The electronic device forming step can include a wiring layer forming step. The electronic device forming step may further include a semiconductor substrate mounting step, a sealing step, a grinding step, and the like. Further, the electronic device forming step may be a step in which the semiconductor substrate is placed on the support via the adhesive composition layer of the encapsulant sealed with the encapsulant.

The adhesive layer forming step can be performed in the same manner as in the method for producing a laminate according to the third aspect.

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

According to the method for manufacturing a laminated body according to the third to fifth aspects, the support and the semiconductor substrate or the electronic device are temporarily bonded to each other via an adhesive layer having high heat resistance. A laminated body in which the adhesive layer and the semiconductor substrate or the electronic device are laminated in this order can be stably manufactured. Such a laminate is a laminate produced in a process based on a fan-out type technology in which terminals provided on a semiconductor substrate are mounted on a wiring layer extending outside the chip area.

(Manufacturing method of electronic parts)
In the method for producing an electronic component according to a sixth aspect of the present invention, after obtaining a laminate by the method for producing a laminate according to any one of the third to fifth aspects, the urethane bond of the urethane resin is acidified. Alternatively, it is characterized by having a step of removing the adhesive layer (hereinafter, also referred to as "adhesive layer removing step") by decomposing with alkali.
When the support is composed of the support substrate and the separation layer, the method according to the present embodiment irradiates the separation layer with light through the support substrate before the adhesive layer removing step to irradiate the separation layer with light. It may further have a separation step of separating the electronic device and the support substrate by altering the quality of the device.

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

[Separation process]
When the support has a separation layer, the method of manufacturing an electronic component according to the present field form may include a separation step. The separation step in the present embodiment is a step of separating the support substrate 1 from the electronic device 456 by irradiating the separation layer 2 with light (arrow) via the support substrate 1 to change the quality of the separation layer 2.
As shown in FIG. 8A, in the separation step, the separation layer 2 is altered by irradiating the separation layer 2 with light (arrows) via the support substrate 1.

Examples of the wavelength at which the separation layer 2 can be altered include a range of 600 nm or less.
The type and wavelength of the light to be irradiated may be appropriately selected according to the transparency of the support substrate 1 and the material of the separation layer 2. For example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and a fiber. It is possible to use solid-state lasers such as lasers, liquid lasers such as dye lasers _{, gas lasers such as CO 2} lasers, excima lasers, Ar lasers and He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, and non-laser light. can. As a result, the separation layer 2 can be altered so that the support substrate 1 and the electronic device 456 can be easily separated.

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

After irradiating the separation layer 2 with light (arrow) to change the quality of the separation layer 2, the support substrate 1 is separated from the electronic device 456 as shown in FIG. 8 (b).
For example, the support base 1 and the electronic device 456 are separated by applying a force in a direction in which the support base 1 and the electronic device 456 are separated from each other. Specifically, one of the support substrate 1 or the electronic device 456 side (wiring layer 6) is fixed to the stage, and the other is lifted while being sucked and held by a separation plate provided with a suction pad such as a bellows pad. The support substrate 1 and the electronic device 456 can be separated.
The force applied to the laminated body 200 may be appropriately adjusted depending on the size of the laminated body 200 and the like, and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, 0.1 to 5 kgf (0). By applying a force of about .98 to 49N), the support substrate 1 and the electronic device 456 can be suitably separated.

When the support does not have a separation layer, the support and the semiconductor substrate or the electronic device can be separated by the adhesive layer removing step described later.

[Adhesive layer removal process]
The method for manufacturing an electronic component according to the present embodiment includes a step of removing an adhesive layer. The adhesive layer removing step is a step of decomposing the crosslinked structure in the adhesive layer with an acid or an alkali to remove the adhesive layer.
In FIG. 8B, the adhesive layer 3 and the separation layer 2 are attached to the electronic device 456 after the separation step. In this step, the adhesive layer 3 and the separation layer 2 are removed by decomposing the adhesive layer 3 with an acid or an alkali to obtain an electronic component 50.

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

The acid or alkali can be dissolved in a solvent and used as a treatment liquid for removing the adhesive layer. The solvent is preferably a polar solvent, and examples thereof include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, and propylene glycol.
The adhesive removing treatment liquid may contain a known additive such as a surfactant in addition to the above components.
The content of the acid or alkali in the treatment liquid is not particularly limited, and examples thereof include 1 to 50% by mass. The content of the polar solvent in the treatment liquid is 50 to 99% by mass.
As the treatment liquid for removing the adhesive layer, a commercially available alkaline treatment liquid or acid treatment liquid may be used. Examples of commercially available treatment solutions include ST-120 and ST-121 (both manufactured by Tokyo Ohka Kogyo Co., Ltd.).
By bringing the above-mentioned treatment liquid containing an acid or an alkali into contact with the adhesive layer 3, the urethane bond of the component (P1) in the adhesive layer 3 is decomposed, and the adhesive layer 3 can be removed.

According to the method for manufacturing an electronic component according to the present embodiment, a semiconductor substrate is obtained by curing the adhesive composition using an adhesive composition containing a urethane resin containing a polymerizable carbon-carbon double bond. Alternatively, the electronic device and the support are temporarily bonded. Therefore, it is possible to form an adhesive layer having high heat resistance that can withstand high temperature treatment in an electronic device forming process or the like. Further, since the urethane resin in the adhesive layer is decomposed by an acid or an alkali, the adhesive layer can be easily washed and removed after the electronic device forming process or the like is completed.

In the method for manufacturing an electronic component of the present embodiment, after the above-mentioned adhesive layer removing step, the electronic component 50 may be further subjected to a treatment such as solder ball formation, dicing, or oxide film formation.

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

<Synthesis example of urethane resin>
(Synthesis Example 1: Urethane Resin (P1) -1)
Propylene glycol monomethyl ether acetate (PGMEA), 33 parts of polycarbonate diol (Mw1,000), 9 parts of polycarbonate diol (Mw500), 18 parts of glycerin monomethacrylate, neo in a flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer. One part of pentyl glycol and a prohibiting agent were added, and the mixture was uniformly mixed under a nitrogen stream. Next, 9 parts of diphenylmethane diisocyanate (hereinafter referred to as "MDI") and 30 parts of hydrogenated xylylene diisocyanate (hereinafter referred to as "H6XDI") were charged into a dropping funnel and added dropwise at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was carried out for 4 to 5 hours. Then, methanol was added and aging was carried out for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared.

(Synthesis Example 2: Urethane Resin (P1) -2)
PGMEA, 13 parts of castor oil modified diol, 29 parts of polycarbonate diol (Mw 1,000), 18 parts of glycerin monomethacrylate, 1 part of neopentyl glycol, and a prohibitive agent in a flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer. Was added and mixed uniformly under a nitrogen stream. Next, 9 parts of MDI and 30 parts of H6XDI were charged in the dropping funnel and dropped at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was carried out for 4 to 5 hours. Then, methanol was added and aging was carried out for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared.

(Synthesis Example 3: Urethane Resin (P1) -3)
In a flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer, PGMEA, 36 parts of castor oil modified diol, 7.5 parts of polycarbonate diol (Mw1,000), 18 parts of glycerin monomethacrylate, 1 part of neopentyl glycol, and A banning agent was added and mixed uniformly under a nitrogen stream. Next, 8 parts of MDI and 29.5 parts of H6XDI were charged into the dropping funnel and dropped at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was carried out for 4 to 5 hours. Then, 2-hydroxyethyl acrylate (2HEA) was added and aged for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared.

(Synthesis Example 4: Urethane Resin (P1) -4)
PGMEA, 48 parts of polycarbonate diol (Mw 1,000), 18 parts of glycerin monomethacrylate, 1 part of neopentyl glycol, and a prohibiting agent are added to a flask equipped with a stirrer, a dropping funnel, a cooling tube, and a thermometer, and the mixture is subjected to a nitrogen stream. Was mixed uniformly with. Next, 6 parts of MDI and 27 parts of H6XDI were charged in the dropping funnel and dropped at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was carried out for 4 to 5 hours. Then, 2HEA was added and aged for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared.

(Synthesis Example 5: Urethane Resin (P1) -5)
PGMEA, 36 parts of castor oil modified diol, 17 parts of polycarbonate diol (Mw 1,000), 18 parts of pentaerythritol diacrylate, 1 part of neopentyl glycol, and prohibited in a flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer. The agent was added and mixed uniformly under a nitrogen stream. Next, 7 parts of MDI and 21 parts of H6XDI were charged in the dropping funnel and dropped at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was carried out for 4 to 5 hours. Then, 2HEA was added and aged for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared.

(Synthesis Example 6: Urethane Resin (P1) -6)
PGMEA, 34 parts of castor oil modified diol, 17 parts of polycarbonate diol (Mw 1,000), 21 parts of pentaerythritol diacrylate, 1 part of neopentyl glycol, and prohibited in a flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer. The agent was added and mixed uniformly under a nitrogen stream. Next, 6 parts of MDI and 21 parts of H6XDI were charged in the dropping funnel and dropped at a constant velocity over 30 minutes. After completion of the dropping, aging was performed for 30 minutes. Then, a bismuth catalyst was added, the temperature was raised to 65 ° C., and aging was carried out for 4 to 5 hours. Then, 2HEA was added and aged for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared.

Table 1 shows the equivalents and weight average molecular weight (Mw) of the polymerizable carbon-carbon double bond contained in the raw materials used for the synthesis of the urethane resins (P1) -1 to (P1) -6 and the urethane resin after the synthesis. Summarized. The numerical values in Table 1 represent the mass ratio. “C = C equivalent” represents the molecular weight (unit: g / eq.) Of the urethane resin per equivalent of the polymerizable carbon-carbon double bond.

In Table 1, each abbreviation has the following meaning.
(O1) -1: Glycerin monomethacrylate.
(O1) -2: Pentaerythritol diacrylate.
(O2) -1: Polycarbonate diol represented by the following formula (PC-1-1) (R =-(CH ₂ ) ₆ -,-(CH ₂ ) _5- ), Mw = 1,000.
(O2) -2: Polycarbonate diol represented by the following formula (PC-1-1) (R =-(CH ₂ ) ₆ -,-(CH ₂ ) _5- ), Mw = 500.

(O2) -3: Castor oil-modified diol (aromatic-containing grade manufactured by Itoh Oil Chemicals, Inc.).
(O2) -4: Neopentyl glycol.
(I) -1: Diphenylmethane diisocyanate.
(I) -2: Hydrogenated xylylene diisocyanate.

<Preparation of adhesive composition>
(Examples 1 to 6, Comparative Examples 1 to 2)
The components shown in Tables 2 and 3 were mixed to prepare an adhesive composition of each example.

In Tables 2 and 3, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).
(P1) -1: Urethane resin (P1) -1 synthesized in the above synthesis example 1.
(P1) -2: Urethane resin (P1) -2 synthesized in Synthesis Example 2 above.
(P1) -3: Urethane resin (P1) -3 synthesized in Synthesis Example 3 above.
(P1) -4: Urethane resin (P1) -4 synthesized in Synthesis Example 4 above.
(P1) -5: Urethane resin (P1) -5 synthesized in Synthesis Example 5 above.
(P1) -6: Urethane resin (P1) -6 synthesized in the above synthesis example 6.
(P2) -1: Epoxy resin (EXA4850-150 (trade name), DIC Corporation).
(P2) -2: Epoxy resin (HP-7200HH (trade name), DIC Corporation).
(A) -1: Peroxide-based thermal polymerization initiator (Park Mill (registered trademark) D, NOF CORPORATION).
(Ad) -1: Polyester-modified polydimethylsiloxane (BYK-310 (trade name), Big Chemie).
(Ad) -2: Thermoacid generator (TAG-2690 (trade name), Kusumoto Kasei Co., Ltd.).
(O2) -5: Polycarbonate diol (Duranol T5650J (trade name), Asahi Kasei Corporation).
(S) -1: PGMEA.

<Evaluation>
≪Applicability≫
The adhesive compositions of each example were coated on the Si substrate by the spin coater method with a film thickness of 50 μm. After application, it was observed with the naked eye and evaluated according to the following evaluation criteria. The results are shown in Table 4 as "applicability".
Evaluation criteria 〇: No spots or voids ×: With spots or voids

≪Measurement of elastic modulus≫
The adhesive compositions of each example were applied onto the Si wafer by the spin coater method, and cured by heating at 180 ° C. for 60 minutes in an oven under a nitrogen atmosphere (film thickness 50 μm). A test piece (thickness 50 μm, width 5 mm, length 40 mm) of the cured film of the adhesive composition was cut out, and using Rheogel-E4000 (manufactured by UBM) at a frequency of 1 Hz, in the range of 50 to 300 ° C. The tensile elastic modulus was measured.

≪Heat resistance test≫
The adhesive compositions of each example were applied onto the semiconductor substrate by the spin coating method to form an adhesive composition layer (thickness: 50 μm). Next, a glass support substrate (diameter 200 cm, thickness 760 μm) was laminated on the adhesive composition layer. This laminate was heated at 180 ° C. for 1 hour in an oven under a nitrogen atmosphere to cure the adhesive composition layer to form an adhesive layer. The laminate consisting of the glass support substrate, the adhesive layer, and the semiconductor substrate was heated at 200 ° C. for 4 hours in an oven under a nitrogen atmosphere. The laminated body after heating was observed with the naked eye and evaluated according to the following evaluation criteria. The results are shown in Table 4 as "heat resistance".
Evaluation criteria 〇: No voids, cracks ×: With voids, cracks

≪Die bond≫
The adhesive compositions of each example were applied onto the Si substrate by the spin coater method, and heated in an oven under a nitrogen atmosphere at 180 ° C. for 1 hour to form an adhesive layer. Using a desktop die bonder T-3000-FC3 set at a stage temperature of 60 ° C. and a bonder terminal temperature of 380 ° C., a Si chip cut into 2 mm × 2 mm was pressed against this adhesive layer with a force of 1.67 N for 10 seconds. Then, the Si chip was peeled off, and the depth of the adhesive layer pushed by the Si chip was measured. The results are shown in Table 4 as "Die bond". If the pushing amount is 0.5 μm or less, it is judged that there is no problem.

≪Cleanability≫
The adhesive compositions of each example were applied onto the Si substrate by the spin coater method, and heated at 180 ° C. for 1 hour in an oven under a nitrogen atmosphere to form an adhesive layer. The Si substrate on which the adhesive layer was formed was immersed in an alkali-containing cleaning solution (ST-120 (trade name), manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 70 ° C., and the dissolution rate of the adhesive layer was measured. The dissolution rate was evaluated according to the following evaluation criteria, and the results are shown in Table 4 as "cleanability".
Evaluation Criteria 〇: Dissolution rate 50 nm / sec or more ×: Dissolution rate less than 50 nm / sec

From the results shown in Table 4, the adhesive layer formed by using the adhesive compositions of Examples 1 to 6 has an elastic modulus as compared with the adhesive layer formed by using the adhesive compositions of Comparative Examples 1 and 2. It was confirmed that it was excellent in heat resistance and detergency.

<Preparation of adhesive composition>
(Examples 7 to 17)
The components shown in Table 5 were mixed to prepare the adhesive compositions of each example.

In Table 5, (B) -1 to (B) -10 have the following meanings, respectively. (P1) -5, (A) -1, (Ad) -1, and (S) -1 are the same as described above. The value in [] is the blending amount (part by mass).
(B) -1: Glycydoxypropyltrimethoxysilane (OFS-6040 (trade name), Dow Toray Co., Ltd.).
(B) -2: 3-methacryloxypropyltrimethoxysilane (KBM-503 (trade name), Shin-Etsu Chemical Co., Ltd.).
(B) -3: Vinyl trimethoxysilane (KBM-1003 (trade name), Shin-Etsu Chemical Co., Ltd.).
(B) -4: One-end reactive silicone oil (X-22-2475 (trade name), Shin-Etsu Chemical Co., Ltd.).
(B) -5: 8-glycidoxyoctyltrimethoxysilane (KBM-4803 (trade name), Shin-Etsu Chemical Co., Ltd.).
(B) -6: N-2- (aminoethyl) -8-aminooctyltrimethoxysilane (KBM-6803 (trade name), Shin-Etsu Chemical Co., Ltd.).
(B) -7: Polymer-type polyfunctional epoxysilane coupling agent (hydrolyzable group: ethoxy group, functional group; epoxy group, functional group equivalent (vs. Si (OR) ₃ ): 3; X-12-981S ( Product name), Shin-Etsu Chemical Industry Co., Ltd.).
(B) -8: Polymer-type polyfunctional isocyanate silane coupling agent (hydrolyzable group: methoxy group, functional group; isocyanate group, functional group equivalent (vs. Si (OR) ₃ ): 2; X-12-1159L ( Product name), Shin-Etsu Chemical Industry Co., Ltd.).

<Evaluation>
≪Peel strength against Si substrate≫
The adhesive compositions of Examples 5 and 7 to 17 were respectively applied onto the Si substrate by the spin coating method, and heated at 100 ° C. for 10 minutes to form an adhesive composition layer (film thickness 50 μm). The adhesive composition layer was then cured by heating in an oven under a nitrogen atmosphere at 180 ° C. for 1 hour to form a test sample. Next, the test sample was cut at 1 cm intervals, and the formed 1 cm wide region was peeled from the Si substrate by the adhesive / film peeling analyzer VPA-H200 (manufactured by Kyowa Kaijo Kagaku Co., Ltd.). The force required for was measured. The results are shown in Table 6 as "peel strength (Si substrate)".

≪Peel strength against molded circuit board≫
Peel strength is increased by the same method as << Peel strength with respect to Si substrate >> except that the adhesive compositions of Examples 5 and 7 to 17 are each applied on a molded substrate containing an epoxy resin and a silica filler by a spin coating method. It was measured. The results are shown in Table 6 as "peel strength (molded substrate)".

From the results shown in Table 6, the adhesive layer formed by using the adhesive compositions of Examples 7 to 13, 15 and 17 was compared with the adhesive layer formed by using the adhesive composition of Example 5. It was confirmed that the adhesion to the Si substrate was improved. Further, the adhesive layer formed by using the adhesive compositions of Examples 7 to 10, 14 and 16 has adhesiveness to the molded substrate as compared with the adhesive layer formed by using the adhesive composition of Example 5. Was confirmed to improve.

≪Heat resistance test≫
The adhesive compositions of Examples 5, 7 to 10, 14, 16 and 17 are respectively applied onto a molded substrate containing an epoxy resin and a silica filler by a spin coating method, and heated at 100 ° C. for 10 minutes to bond them. An agent composition layer was formed (thickness: 50 μm). Next, a glass support having a separation layer was laminated on the adhesive composition layer. Under the temperature condition of 50 ° C., the pressure was applied at 140 kgf for 150 seconds, and further heated at 100 ° C. for 5 minutes to bond the substrate and the glass support. The adhesive composition layer was cured by heating at 180 ° C. for 1 hour in an oven under a nitrogen atmosphere to form an adhesive layer. It was then heated at 230 ° C. for 1 or 2 hours in an oven under a nitrogen atmosphere. The laminated body after heating was observed with the naked eye and evaluated according to the following evaluation criteria. The results are shown in Table 7 as "heat resistance". In Example 5, since voids were observed under the condition of 230 ° C. for 1 hour, no further measurement was carried out.
Evaluation Criteria A: Voids, no cracks B: Slightly observed voids and cracks C: Many voids and cracks are observed

From the results shown in Table 7, the adhesive layer formed by using the adhesive compositions of Examples 7 to 10, 14, 16 and 17 was compared with the adhesive layer formed by using the adhesive composition of Example 5. It was confirmed that the heat resistance was improved.

1 Support base 2 Separation layer 3 Adhesive layer 3'Adhesive composition layer 4 Semiconductor substrate 5 Encapsulant layer 6 Wiring layer 12 Support 20 Laminated body 50 Electronic components 100 Laminated body 100' Laminated body 110 Laminated body 120 Laminated body 200 Laminated body 300 Laminated body 400 Laminated body 456 Electronic device 645 Electronic device

Claims (11)

An adhesive composition used for forming an adhesive layer that temporarily adheres a semiconductor substrate or an electronic device to a support.
A urethane resin containing a polymerizable carbon-carbon double bond, a polymerization initiator, and
An adhesive composition containing. The urethane resin is a reaction product of a polyol and a polyisocyanate.
At least one of the polyol and the polyisocyanate comprises the polymerizable carbon-carbon double bond.
The adhesive composition according to claim 1. The electronic device is characterized in that a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member is laminated on the support via the adhesive layer. The adhesive composition according to claim 1 or 2. The adhesive composition according to any one of claims 1 to 3, further comprising a silane coupling agent. A laminate in which a support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order.
The adhesive layer is a cured product of the adhesive composition according to any one of claims 1 to 4.
Laminated body. The support is composed of a support substrate that transmits light and a separation layer that is altered by irradiation with light, and the adhesive layer is adjacent to the separation layer.
The laminate according to claim 5. A method for manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order.
A step of applying the adhesive composition according to any one of claims 1 to 4 to the support or a semiconductor substrate to form an adhesive composition layer.
A step of placing the semiconductor substrate on the support via the adhesive composition layer, and
A step of curing the adhesive composition layer by a polymerization reaction of the urethane resin to form the adhesive layer, and a step of forming the adhesive layer.
A method for producing a laminated body. After obtaining a laminate by the method for producing a laminate according to claim 7, an electronic device is formed, which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Has more steps to
A method for manufacturing a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order. The support is composed of a support substrate that transmits light and a separation layer that is altered by irradiation with light, and in the laminate, the adhesive layer is adjacent to the separation layer.
The method for producing a laminate according to claim 8. After obtaining the laminate by the method for producing the laminate according to claim 8,
It has a step of removing the adhesive layer by decomposing the urethane bond of the urethane resin with an acid or an alkali.
Manufacturing method of electronic parts. After obtaining the laminate by the method for producing the laminate according to claim 9,
A step of separating the electronic device and the support substrate by irradiating the separation layer with light through the support substrate and altering the separation layer.
A step of removing the adhesive layer adhering to the electronic device by decomposing the urethane bond of the urethane resin with an acid or an alkali.
A method for manufacturing electronic components.

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