KR20230165141A - Adhesive composition, laminate, manufacturing method of laminate, and manufacturing method of electronic component - Google Patents

Abstract

[Problem] An adhesive composition that can suppress the occurrence of delamination due to a high temperature process and has good cleaning properties of the adhesive layer, a laminate manufactured using the adhesive composition, a method for manufacturing the laminate, and a method using the adhesive composition. Provides a manufacturing method for electronic components.
[Solution] An adhesive composition used to form an adhesive layer that temporarily bonds a semiconductor substrate or electronic device to a light-transmitting support, comprising a urethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond, and caprolactone. An adhesive composition containing modified urethane acrylate (M1) and a polymerization initiator (A).

Description

Adhesive composition, laminate, method of manufacturing laminate, and method of manufacturing electronic component {ADHESIVE COMPOSITION, LAMINATE, MANUFACTURING METHOD OF LAMINATE, AND MANUFACTURING METHOD OF ELECTRONIC COMPONENT}

The present invention relates to adhesive compositions, laminates, methods for manufacturing laminates, and methods for manufacturing electronic components.

Semiconductor packages (electronic components) containing semiconductor elements exist in various forms depending on the corresponding size, for example, wafer level package (WLP), panel level package (PLP), etc.

Semiconductor package technologies include fan-puppet technology and fan-out type technology. As a semiconductor package using fan-puppet technology, a fan-puppet WLP (Fan-in Wafer Level Package), which rearranges the terminals at the end of the bare chip within the chip area, is known. As a semiconductor package using fan-out technology, a fan-out type WLP (Fan-out Wafer Level Package) in which the terminal is relocated outside the chip area is known.

Recently, in particular, fan-out type technology has been applied to fan-out type PLP (Fan-out Panel Level Package), which packages semiconductor elements by arranging them on a panel, and has led to further high integration, thinning, and miniaturization of semiconductor packages. It is attracting attention as a method that can realize this.

In order to achieve miniaturization of semiconductor packages, it becomes important to reduce the thickness of the substrate for the assembled elements. However, if the thickness of the substrate is thinned, its strength decreases, making it easy for the substrate to be damaged during semiconductor package manufacturing. In relation to this, a technique is known in which a substrate is temporarily attached to a support using an adhesive, the substrate is processed, and then the substrate and the support are separated.

As an adhesive used for temporary adhesion between a substrate and a support, a thermoplastic adhesive is often used because the adhesive layer is easy to remove 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.

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

However, in the manufacture of semiconductor packages, high-temperature treatments such as thin film formation, firing, and die bonding are applied. If the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer may decrease during high temperature treatment, resulting in delamination. On the other hand, adding a crosslinking agent to the adhesive increases the elastic modulus of the adhesive layer and improves heat resistance. However, after separating the substrate from the support, the cleanability of the adhesive layer attached to the substrate significantly decreases.

The present invention has been made in consideration of the above circumstances, and provides an adhesive composition that can suppress the occurrence of delamination due to a high temperature process and has good cleaning properties of the adhesive layer, a laminate manufactured using the adhesive composition, and a laminate of the laminate. The object is to provide a manufacturing method and a manufacturing method of electronic components using the adhesive composition.

In order to solve the above problems, the present invention adopts the following configuration.

That is, the first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device and a light-transmitting support, comprising a urethane resin containing a polymerizable carbon-carbon unsaturated bond. It is an adhesive composition containing (P1), caprolactone-modified urethane acrylate (M1), and a polymerization initiator (A).

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

A third aspect of the present invention is a method of manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, wherein the adhesive composition according to the first aspect is applied to the support or the semiconductor substrate to form an adhesive composition layer. A method of manufacturing a laminate comprising a step of forming a step, a step of placing the semiconductor substrate on the support through the adhesive composition layer, and a step of curing the adhesive composition layer to form the adhesive layer.

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

The fifth aspect of the present invention is to remove the adhesive layer by decomposing the urethane bond of the urethane resin with an acid or alkali after obtaining the laminate by the method for manufacturing a laminate according to the fourth aspect. It is a manufacturing method of electronic components that includes a process.

According to the present invention, an adhesive composition that can suppress the occurrence of delamination due to a high temperature process and has good cleaning properties of the adhesive layer, a laminate manufactured using the adhesive composition, a method for producing the laminate, and the adhesive composition A method of manufacturing electronic components using is provided.

[Figure 1] A schematic diagram showing one embodiment of a laminate to which the present invention is applied.
[Figure 2] A schematic diagram showing one embodiment of a laminate to which the present invention is applied.
[Figure 3] A schematic diagram showing one embodiment of a laminate to which the present invention is applied.
[Figure 4] is a schematic diagram showing one embodiment of a laminate to which the present invention is applied.
[FIG. 5] is a schematic process diagram illustrating one embodiment of a method for manufacturing a laminate 100' in which a support, an adhesive composition layer, and a semiconductor substrate are laminated in this order. FIG. 5(a) is a diagram showing a support consisting of a support base and a separation layer, FIG. 5(b) is a diagram explaining the adhesive composition layer forming process, and FIG. 5(c) is a diagram showing a semiconductor substrate. This is a drawing explaining the tact process.
[Figure 6] A diagram explaining the adhesive layer forming process.
[FIG. 7] is a schematic process diagram explaining one embodiment of a method for manufacturing the laminate 120. FIG. 7(a) is a diagram explaining the encapsulation process, FIG. 7(b) is a diagram explaining the grinding process, and FIG. 7(c) is a diagram explaining the wiring layer forming process.
[FIG. 8] is a schematic process diagram explaining one embodiment of a method for manufacturing a semiconductor package (electronic component) from the laminate 120. FIG. 8(a) is a diagram showing the laminate 200, FIG. 8(b) is a diagram explaining the separation process, and FIG. 8(c) is a diagram explaining the adhesive layer removal process.

In this specification and the claims of this patent, “aliphatic” is a relative concept to aromatic, and is defined to mean a group, compound, etc. that does not have aromaticity.

Unless otherwise specified, “alkyl group” includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups among alkoxy groups.

Unless otherwise specified, the “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups.

A “halogenated alkyl group” is a group in which some or all of the hydrogen atoms of an alkyl group are replaced with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which some or all of the hydrogen atoms of an alkyl group or alkylene group are replaced with fluorine atoms.

“Structural unit” means a monomer unit (monomer unit) that constitutes a high molecular compound (resin, polymer, copolymer).

When stating “You may have a substituent” or “You may have a substituent”, when the hydrogen atom (-H) is replaced with a monovalent group, and when the methylene group (-CH ₂ -) is replaced with a divalent group includes both sides.

“Structural unit derived from hydroxystyrene” means a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. “Structural unit derived from a hydroxystyrene derivative” means a structural unit formed by cleavage of the ethylenic double bond of a hydroxystyrene derivative.

“Hydroxystyrene derivatives” is a concept that includes those in which the hydrogen atom in the α position of hydroxystyrene is replaced by other substituents such as an alkyl group and a halogenated alkyl group, and derivatives thereof. These derivatives include those obtained by replacing the hydrogen atom of the hydroxyl group of hydroxystyrene, where the hydrogen atom on α may be substituted with a substituent, with an organic group; Examples include those in which a substituent other than a hydroxyl group is bonded to the benzene ring of hydroxystyrene, where the hydrogen atom on α may be substituted with a substituent. In addition, the α position (carbon atom on α) refers to the carbon atom to which the benzene ring is bonded, unless otherwise specified.

Substituents that replace the hydrogen atom on α of hydroxystyrene include the same substituents listed as the substituent on α in the α-substituted acrylic acid ester.

The alkyl group as the substituent on α is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, iso). butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group), etc.

In addition, the halogenated alkyl group as the substituent on α specifically includes a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent on α” above are replaced with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable.

In addition, the hydroxyalkyl group as the substituent on α specifically includes a group in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent on α” are replaced with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

In the present specification and the claims of this patent, depending on the structure represented by the chemical formula, an asymmetric carbon may exist and an enantiomer or a lower stereoisomer may exist, but in that case, represents these isomers in one formula. These isomers may be used individually or as a mixture.

(Adhesive composition)

The adhesive composition according to the first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device and a support, and is composed of a urethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond. ), caprolactone-modified urethane acrylate (M1), and a polymerization initiator (A).

<Target of temporary adhesion>

The adhesive composition according to this embodiment is used to form an adhesive layer that temporarily bonds a semiconductor substrate or electronic device and a support. In this specification, “temporary adhesion” refers to temporary adhesion of the object to be adhered (for example, between arbitrary work processes). More specifically, the semiconductor substrate or electronic device is temporarily bonded to a support and fixed on the support for thinning of the device, transportation of the semiconductor substrate, mounting on the semiconductor substrate, etc. (temporary bonding), After completion of the process, it is separated from the support.

≪Semiconductor substrate≫

The semiconductor substrate to which the adhesive composition according to this embodiment is applied is not particularly limited, and may be one generally used as a semiconductor substrate. A semiconductor substrate (bare chip) is supported on a support body and subjected to processes such as thinning and mounting. For example, structures such as integrated circuits or metal bumps may be mounted on the semiconductor substrate.

The semiconductor substrate typically includes a silicon wafer substrate, but is not limited to this and may also be a ceramic substrate, thin film substrate, or flexible substrate.

≪Electronic device≫

In this specification, “electronic device” means a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited and may be one in which various mechanical structures or circuits are formed on the surface of a semiconductor substrate. The electronic device may preferably be a composite of a member made of 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 an encapsulating material or an insulating material, and may have a single-layer or multi-layer structure.

≪Support≫

A support body is a member that supports a semiconductor substrate or electronic device. As will be described later, the support may be composed of a support base that has the characteristic of transmitting light and is a member that supports the semiconductor substrate, and a separation layer that deteriorates by irradiation of light.

<Urethane resin containing polymerizable carbon-carbon double bond: (P1) component>

The adhesive composition according to this embodiment contains a urethane resin containing a polymerizable carbon-carbon double bond (hereinafter also referred to as “(P1) component”). The (P1) component can be polymerized and cured by a polymerizable carbon-carbon double bond to form an adhesive layer. Thereby, the semiconductor substrate or electronic device and the support can be temporarily bonded. Additionally, the urethane bond in component (P1) has the property of being decomposed by acid or alkali. Therefore, the adhesive layer can be easily removed with a treatment liquid containing acid or alkali. Those corresponding to the (M) component described later are excluded from the (P1) component.

The polymerizable carbon-carbon double bond contained in the component (P1) is not particularly limited, but is preferably radically polymerizable. Examples of polymerizable carbon-carbon double bonds include methacryloyl group and acryloyl group. (P1) The number of polymerizable carbon-carbon double bonds contained in the component may be one, or two or more types may be used.

The equivalent weight of the polymerizable carbon-carbon double bond contained in the component (P1) is preferably 200 to 2000 g/eq., more preferably 300 to 1500 g/eq., and even more preferably 400 to 1200 g/eq. is preferred, and 500 to 1000 g/eq. is particularly preferred. If the polymerizable carbon-carbon double bond equivalent is more than the lower limit of the above preferred range, the elastic modulus, heat resistance, etc. of the adhesive layer are further improved. If the polymerizable carbon-carbon double bond equivalent is below the upper limit of the above preferred range, the adhesive layer will not become too hard and cleanability will be good. The equivalent number is the molecular weight of the urethane resin per equivalent of a polymerizable carbon-carbon double bond.

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

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

≪Polyisocyanate compound: (I) component≫

In this specification, “polyisocyanate compound” means a compound (polyisocyanate) having two or more isocyanate groups (-N=C=O) or a compound (block polyisocyanate) having two or more blocked isocyanate groups. . There is no particular limitation on the polyisocyanate, and those generally used in the production of urethane resins can be used without particular limitation.

Blocked polyisocyanate is a compound in which the isocyanate group of polyisocyanate is blocked by reaction with a blocking agent and is inactivated. (I) The blocked polyisocyanate used as component is preferably one in which the isocyanate group is blocked by a thermally dissociable blocking agent. Examples of thermally dissociable blocking agents include blocking agents such as oximes, diketones, phenols, and caprolactams. In the blocked polyisocyanate made by a thermally dissociable blocking agent, the isocyanate group is inactive at room temperature, and when heated, the thermally dissociable blocking agent dissociates and regenerates the isocyanate group.

Specific examples of polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. ; and tolylene diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,4'-diphenyl methane diisocyanate, naphthalene diisocyanate, xylene diisocyanate, tricyne diisocyanate, p-phenylene diisocyanate, naphthylene. Aromatic diisocyanates such as diisocyanate; and their biuret form, isocyanurate form, and adduct form of trimethylolpropane. Polyisocyanate may be used individually by 1 type, or may use 2 or more types together.

As polyisocyanate, you may use a commercially available one. Commercially available polyisocyanates include, for example, Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, Duranate MHG-80B, Duranate TUL-100, Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405- 70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (above, brand name, discontinued by Asahi Kasei Chemicals). These products may be used individually, or two or more types may be used together.

Examples of the blocked isocyanate include compounds in which the isocyanate group of the above polyisocyanate is protected by reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermally dissociable blocking agent, that is, a compound that is added to an isocyanate group and is stable at room temperature, but is free when heated above the dissociation temperature to generate an isocyanate group, and a known one can be used without particular limitation.

Specific examples of blocking agents include lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; oxime compounds such as methyl ethyl keto oxime, methyl isoamyl keto oxime, methyl isobutyl keto oxime, formamide oxime, acetoamide oxime, aceto oxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime; Monocyclic phenol compounds such as phenol, cresol, catechol, and nitrophenol; polycyclic phenol compounds such as 1-naphthol; alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, trimethylolpropane, and 2-ethylhexyl alcohol; Ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; Active methylene compounds such as malonic acid alkyl ester, malonic acid dialkyl ester, acetoacetic acid alkyl ester, and acetylacetone; etc. can be mentioned. One type of blocking agent may be used individually, or two or more types may be used together.

Blocked polyisocyanate can be produced by reacting polyisocyanate with a blocking agent. The reaction between polyisocyanate and blocking agent can be carried out, for example, in a solvent without active hydrogen (1,4-dioxane, cellosolve acetate, etc.) under heating at about 50 to 100°C and, if necessary, with a blocking catalyst. performed in the presence of The use ratio of polyisocyanate and blocking agent is not particularly limited, but is preferably 0.95:1.0 to 1.1:1.0, more preferably 1:1.05 to 1.15, as the equivalent ratio of isocyanate groups in polyisocyanate to blocking agent. As the blocking catalyst, known catalysts can be used, for example, metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate, and potassium methylate; Hydrooxides of tetraalkyl ammonium such as tetramethyl ammonium, tetraethyl ammonium, and tetrabutyl ammonium; weak organic acid salts thereof such as acetic acid, octylate, myristic acid, and benzoic acid; and alkali metal salts of alkyl carboxylic acids such as acetic acid, caproic acid, octylic acid, and myristic acid; etc. can be mentioned. Blocking catalysts may be used individually or in combination of two or more types.

As the blocked polyisocyanate, you may use a commercially available one. Commercially available block polyisocyanates include, for example, Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Duranate. E402-B80B (above, brand name, manufactured by Asahi Kasei Co., Ltd.), etc. can be mentioned.

As the component (I), a blocked polyisocyanate in which the isocyanate group is blocked by a thermally dissociable blocking agent is preferable.

(I) Component may be used individually by 1 type, or may use 2 or more types together. For example, component (I) can be a mixture of aliphatic diisocyanate and aromatic diisocyanate. As the aliphatic diisocyanate, hydrogenated xylene diisocyanate is preferable. As the aromatic diisocyanate, 4,4-diphenyl methane diisocyanate is preferable.

≪Polyol: (O) component≫

Polyol ((O) component) is a compound having two or more hydroxy groups (-OH). There is no particular limitation on the polyol, and those generally used in the production of urethane resins can be used without particular limitation. Examples of the (O) component include polyols containing polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as “(O1) component”) and other polyols (hereinafter also referred to as “(O2) component”). can be mentioned.

·Polyol containing polymerizable carbon-carbon unsaturated bonds ((O1) component)

As the (O1) component, a polyol containing at least one type selected from the group consisting of a methacryloyl group and an acryloyl group can be mentioned. (O1) The number of polymerizable carbon-carbon unsaturated bonds contained in the component may be one or two or more.

Examples of the (O1) component include polyols having trivalence or higher, and esters of methacrylic acid, acrylic acid, or derivatives thereof. As the trivalent or higher polyol, a trivalent or higher low molecular weight polyol is preferable. Examples of the trihydric or higher low molecular weight polyol include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylol methane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; Hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; heptahydric alcohols such as perseitol; and octahydric alcohols such as sucrose; etc. can be mentioned.

Specific examples of the (O1) component include glycerol mono(meth)acrylate, diglycerol tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, and diglycerol di(meth)acrylate. ) Acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth) Acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, etc. are mentioned.

“(Meth)acrylate” is a concept including methacrylate and acrylate, and means methacrylate or acrylate.

(O1) Component may be used individually by 1 type, or 2 or more types may be used together.

Among these, the (O1) component is preferably a diol containing a methacryloyl group or an acryloyl group, and glycerol mono(meth)acrylate or pentaerythritol di(meth)acrylate is more preferable.

·Other polyols ((O2) component)

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

Low molecular weight polyols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, and 1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, alkanediol with 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl- 2-Butyl-1,3-propanediol, alkane-1,2-diol with 17 to 20 carbon atoms, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,4-cyclohexane diols, dihydric alcohols such as hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, and bisphenol A; Trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylol methane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; Hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; heptahydric alcohols such as perseitol; and octahydric alcohols such as sucrose; etc. can be mentioned.

Among them, the low molecular weight polyol is preferably a dihydric alcohol (diol).

Examples of polymer polyols include phenol resins, resins containing a hydroxystyrene skeleton, polyester polyols, polyether polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, Polyurethane polyol, vegetable oil-based polyol, etc. are mentioned. The number average molecular weight of the polymer polyol is preferably 500 to 100,000.

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

[Phenolic resin]

The phenol resin may be a novolak-type phenol resin or a resol-type phenol resin. A novolak-type phenol resin can be obtained by causing addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as “phenols”) and an aldehyde under an acid catalyst. A resol-type phenol resin can be obtained by addition condensation of phenols and aldehydes under an alkali catalyst.

Examples of the phenols include phenol; Cresols such as m-cresol, p-cresol, and o-cresol; Xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol; m-ethylphenol, p-ethyl phenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- Alkyl phenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol; Alkoxy phenols such as p-methoxy phenol, m-methoxy phenol, p-ethoxy phenol, m-ethoxy phenol, p-propoxy phenol, and m-propoxy phenol; Isopropenyl phenols such as o-isopropenyl phenol, p-isopropenyl phenol, 2-methyl-4-isopropenyl phenol, and 2-ethyl-4-isopropenyl phenol; Aryl phenols such as phenylphenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis and polyhydroxyphenols such as (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-phenyl propyl aldehyde, β-phenyl propyl aldehyde, o-hydroxybenz aldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methyl benzaldehyde, m-methyl benzaldehyde, p-methyl benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, Examples include cinnamaldehyde, 4-isopropyl benz aldehyde, 4-isobutyl benz aldehyde, and 4-phenyl benz aldehyde.

The acid catalyst during the addition condensation reaction is not particularly limited, and for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. are used. The alkaline catalyst during the addition condensation reaction is not particularly limited, and sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, sodium carbonate, hexamethylenetetramine, etc. are used.

[Resin containing hydroxystyrene skeleton]

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

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

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

The alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically includes methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, Isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are replaced with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable.

As R, a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a fluorinated alkyl group with 1 to 5 carbon atoms is preferable, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

In the above formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.

Suitable examples of the divalent linking group for Ya ^x1 include a divalent hydrocarbon group that may have a substituent, and a divalent linking group containing a hetero atom.

· Divalent hydrocarbon group that may have a substituent:

When Ya ^x1 is a divalent hydrocarbon group that 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 refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing a ring in the structure.

···Line-chain or branched-chain aliphatic hydrocarbon group

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. do.

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 -], etc.

The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, more 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 )-, -C(CH ₃ ) ₂ -, -C Alkyl methylene groups such as (CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) _2- ; -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 ethylene groups such as; Alkyl trimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -; Alkyl alkylene groups such as alkyl tetramethylene groups such as -CH(CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ ) CH2CH2-, etc. are mentioned. As the alkyl group in the alkyl alkylene 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, and a carbonyl group.

···Aliphatic hydrocarbon group containing a ring in the structure

Examples of the aliphatic hydrocarbon group containing a ring in the above structure include a cyclic aliphatic hydrocarbon group (group with two hydrogen atoms removed from the aliphatic hydrocarbon ring) which may contain a substituent containing a hetero atom in the ring structure, and the above-mentioned cyclic aliphatic hydrocarbon group. Examples include a group bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon groups described above include those similar to those described above.

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

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. 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 include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from the polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane and norbornane. , isobornane, tricyclodecane, tetracyclododecane, etc.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group are more preferable. , methoxy group, and ethoxy group are most preferred.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are replaced with the halogen atoms.

In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, and -S(=O) ₂ -O- are preferable.

··Aromatic hydrocarbon group in Ya ^x1

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

This aromatic ring is not particularly limited as long as it is a cyclic conjugate system having 4n+2 pi electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and especially preferably 6 to 12 carbon atoms. However, the number of carbon atoms mentioned above does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocycle in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include groups obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or hetero arylene group); A group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); A group in which one hydrogen atom of a group (aryl group or heteroaryl group) excluding one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naph) and a group in which one hydrogen atom is further removed from the aryl group in an aryl alkyl group such as tylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group. The number of carbon atoms of the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and especially preferably 1 carbon atom.

As for the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.

Examples of the alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those exemplified as substituents that replace the hydrogen atom of the cyclic aliphatic hydrocarbon group.

·Divalent linking group containing a hetero atom:

When ^Ya -, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H may be substituted with a substituent such as an alkyl group or acyl group.), -S-, -S( =O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C( =O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O ) A group represented by ₂ -OY ²² - [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group that may have a substituent, O is an oxygen atom, and m" is an integer of 0 to 3.] etc. can be mentioned.

The divalent linking group containing the above hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- In the case of , H may be substituted with a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and especially preferably 1 to 5 carbon atoms.

General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O )-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) ₂ -OY ²² -, Y ²¹ and Y ²² are each independent It is a divalent hydrocarbon group that may have a substituent. Examples of the divalent hydrocarbon group include those similar to (divalent hydrocarbon group that may have a substituent) mentioned in the description of the divalent linking group above.

As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group with 1 to 5 carbon atoms is still more preferable, and a methylene group or an ethylene group is particularly 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 alkyl methylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

In the group represented by the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. And 1 is particularly preferable. That is, as the group represented by the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² -, the group represented by the formula -Y ²¹ -C(=O)-OY ²² - is particularly preferable. Among them, , a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferred. In the above formula, a' is an integer of 1 to 10, and is a group of 1 to 8. An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is still more preferable, and 1 is most preferable. b' is an integer of 1 to 10, and an integer of 1 to 8 is preferable, and 1 An integer of ~5 is more preferred, 1 or 2 is more preferred, and 1 is most preferred.

^As Ya A combination of the above is preferable, and a single combination is particularly more preferable.

In the above formula (a10-1), Wa ^x1 is a (n _ax1 +1) valent aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group in Wa ^x1 include groups in which (n _ax1 +1) hydrogen atoms have been removed from the aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugate system having 4n+2 pi electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and especially preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocycle in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. 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.

Below, specific examples of structural units represented by the general formula (a10-1) are shown.

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 is more preferably a polymer of hydroxystyrene (polyhydroxystyrene).

[polycarbonate polyol]

Examples of polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9- Nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, or hydrogenated bisphenol A. Alternatively, polycarbonate polyol can be obtained by reacting two or more types of glycols with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc.

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

[In the formula, Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. np is an integer greater than or equal to 2.]

In the general formula (PC-1), Rp ¹ and Rp ² each independently represent a divalent hydrocarbon group. The divalent hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of the divalent hydrocarbon group include those mentioned as Ya ^x1 in the general formula (a10-1). As the divalent hydrocarbon group for 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 especially preferably 500 to 1000.

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

[Other polyols]

Examples of polyester polyols include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebatic acid, dialkyl esters thereof, or mixtures thereof, and such as ethylene glycol, propylene glycol, diethylene glycol, and butyl. Len glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, etc. Polyester polyol that can be obtained by reacting glycols or mixtures thereof, or poly that can be obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone). and ester polyol.

Examples of polyether polyols include oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and oxirane compounds such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin. Examples include polyether polyol, which can be obtained by polymerizing a low-molecular-weight polyol as an initiator.

Examples of polyether ester polyols include polyether esters obtained by reacting dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebatic acid, dialkyl esters thereof, or mixtures thereof with the polyether polyol. Polyols can be mentioned.

Examples of the polyester amide polyol include polyester amide polyols that can be obtained by using, for example, aliphatic diamines having an amino group such as ethylene diamine, propylene diamine, and hexamethylene diamine as raw materials in the esterification reaction. You can.

Acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate, which contain one or more hydroxyl groups in one molecule, or their corresponding methacrylic acid derivatives, such as acrylic acid, methacrylic acid, or the like. Examples include polyester amide polyol, which can be obtained by copolymerizing ester.

Examples of polyhydroxyalkane include butadiene or liquid rubber obtained by copolymerizing butadiene with acrylamide, etc.

The polyurethane polyol is a polyol having one or more urethane bonds in one molecule, for example, polyether polyol, polyester polyol, polyether ester polyol, etc. with a number average molecular weight of 200 to 20,000, and polyisocyanate, preferably Examples include polyurethane polyol that can be obtained by reacting with NCO/OH of less than 1, more preferably 0.9 or less.

Examples of vegetable oil-based polyols 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 using a vegetable oil-based polyol as the (O2) component, the ratio of the vegetable oil-based polyol to the (O1) component (vegetable oil-based polyol/(O1) component (mass ratio)) is preferably 0.1 to 5, and 0.3 to 3. It is more preferable, and 0.4 to 2.5 is further preferable.

(O2) Component may be used individually by 1 type, or 2 or more types may be used together.

Among the above, polycarbonate polyol and low molecular weight polyol are preferable as the (O2) component from the viewpoint of adjusting the viscosity of the adhesive composition and the hardness of the adhesive layer. Additionally, from the viewpoint of improving the heat resistance of the adhesive layer, castor oil-modified polyol may be used as the (O2) component.

The (O) component is preferably a combination of the (O1) component and the (O2) component from the viewpoint of adjusting the viscosity of the adhesive composition and the heat resistance of the adhesive layer. As the (O2) component, low molecular weight polyol, polycarbonate polyol, castor oil-modified polyol, or a combination thereof is preferable. Specific examples of the (O2) component combined with the (O1) component include a combination of polycarbonate polyol, castor oil-modified polyol, and low molecular weight polyol; A combination of polycarbonate polyol and castor oil modified polyol; and polycarbonate polyol.

The mass ratio of the (O1) component and the (O2) component is preferably (O1):(O2)=1:5 to 5:1, more preferably 1:4 to 2:1, and 1:4 to 1:1. 1 is more preferable, and 1:4 to 1:2 is particularly preferable. By keeping the mass ratio of the (O1) component and the (O2) component within the above range, the elastic modulus and heat resistance of the adhesive layer can be improved.

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

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

(P1) Component may be used individually by 1 type, or 2 or more types may be used together.

The content of component (P1) in the adhesive composition of this embodiment is not particularly limited as long as it is a concentration that can be applied to a support or the like. The content of component (P1) in the adhesive composition is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, and 40 to 80% by mass, relative to the total amount (100% by mass) of the adhesive composition. It is more preferable, and 50 to 70 mass% is particularly preferable.

<Cross-linking agent component: (M) component>

The adhesive composition of this embodiment contains a crosslinking agent component (hereinafter also referred to as “(M) component”) in addition to the component (P1). The adhesive composition of this embodiment contains caprolactone-modified urethane acrylate (hereinafter also referred to as “(M1) component”) as a crosslinking agent component.

≪Caprolactone modified urethane acrylate: (M1) ingredient≫

The (M1) component is a urethane acrylate containing a polycaprolactone group (-[O(CH ₂ ) ₅ CO] _n -). Examples of the (M1) component include urethane acrylate containing a group represented by the following general formula (c1).

[Wherein, Rc ¹ represents a hydrogen atom or a methyl group; Rc ² represents an alkylene group; n represents an integer from 1 to 20.]

In the above formula (c1), Rc ² represents an alkylene group. The alkylene group in Rc ² may be linear, branched, or cyclic, but is preferably linear. The alkylene group for Rc ² preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Preferred, and 1 to 3 carbon atoms, or 1 or 2 carbon atoms, are particularly preferable.

In the above formula (c1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and still more preferably an integer of 1 to 6.

The group represented by the above formula (c1) is preferably a group represented by the following formula (c1-1).

[Wherein, Rc ¹ represents a hydrogen atom or a methyl group; m represents an integer from 1 to 10; n represents an integer from 1 to 20.]

In the above formula (c1-1), m is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, further preferably an integer of 1 to 4, and especially preferably an integer of 1 to 3. . Specific examples of m include 2.

In the above formula (c1-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and still more preferably an integer of 1 to 6.

(M1) The main skeleton of urethane acrylate in component is not particularly limited. The urethane acrylate may be of a biuret type, an isocyanurate type, or an adduct type with an aliphatic polyol (for example, trimethylolpropane). Examples of the biuret-type (M1) component include the following general formula (m1-1). Examples of the isocyanurate type (M1) component include the following general formula (m1-2). Examples of the adduct type (M1) component include the following general formula (m1-3).

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

In the above formulas (m1-1) to (m1-3), Rm ¹ , Rm ² , and Rm ³ each independently represent a hydrocarbon group that may have a substituent. Examples of the hydrocarbon group that may have a substituent include those listed as the divalent hydrocarbon group that may have a substituent in Ya ^x1 in the formula (a10-1).

Rm ¹ , Rm ² , and Rm ³ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in Rm ¹ , Rm ² , and Rm ³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms.

The aromatic hydrocarbon group in Rm ¹ , Rm ² , and Rm ³ preferably has 4 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. The aromatic ring contained in the aromatic hydrocarbon group may be an aromatic hydrocarbon ring or an aromatic heterocycle.

The hydrocarbon group in Rm ¹ , Rm ² , and Rm ³ may or may not have a substituent. Substituents that may have a hydrocarbon group for Rm ¹ , Rm ² , and Rm ³ include the same substituents as the divalent hydrocarbon group that may have a substituent for Ya ^x1 in the formula (a10-1) above. there is.

Rm ¹ , Rm ² , and Rm ³ are preferably a linear or branched alkylene group, more preferably a linear alkylene group, and even more preferably a linear alkylene group having 1 to 10 carbon atoms, A linear alkylene group having 1 to 6 carbon atoms is particularly preferable.

In the above formula (m1-3), Rm ⁴ to Rm ⁶ each independently represent a linear or branched alkylene group. The linear alkylene group in Rm ⁴ to Rm ⁶ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, and has more preferably 1 to 6 carbon atoms. 1 to 3 are particularly preferable. The branched alkylene group in Rm ⁴ to Rm ⁶ preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, further preferably 2 to 6 carbon atoms, and has more preferably 2 to 6 carbon atoms. 2 or 3 is particularly preferred.

In the above formula (m1-3), Rm ⁷ represents a linear or branched alkyl group. The linear alkyl group for Rm ⁷ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, and 1 to 3 carbon atoms. Particularly desirable. The branched alkyl group for Rm ⁷ preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, further preferably 3 to 6 carbon atoms, and has 3 or 4 carbon atoms. Particularly desirable.

(M1) Specific examples of the component are given below, but are not limited to these.

[In the formula, Rx ¹¹ to Rx ¹³ represent a group represented by the following formula (c1-1-1).]

[In the formula, n represents an integer from 1 to 20.]

(M1) The component can be obtained by a known method. The (M1) component can be obtained, for example, by reacting caprolactone-modified (meth)acrylate with a polyisocyanate compound.

Examples of the polyisocyanate compound include the same ones as those listed as component (I). Examples of the polyisocyanate compound include the biuret form of diisocyanate, the isocyanurate form of diisocyanate, and the adduct form of diisocyanate and aliphatic polyol (for example, trimethylolpropane). Examples of the biuret form of diisocyanate include compounds represented by the following general formula (I-1). Examples of the isocyanurate form of diisocyanate include compounds represented by the following general formula (I-2). Examples of diisocyanate adducts include compounds represented by the following general formula (I-3).

[In the formula, Rm ¹ to Rm ⁷ are the same as Rm ¹ to Rm ⁷ in the above formulas (m1-1) to (m1-3).]

As diisocyanates for forming the compounds of formulas (I-1) to (I-3), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4 -Diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-di Isocyanate, xylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(methyl isocyanate) cyclohexane, methylcyclohexane diisocyanate, m-tetramethyl xylene diisocyanate, etc. , but is not limited to these. Among them, preferred diisocyanates include tolylene diisocyanate, hexamethylene diisocyanate, 1,3-bis(methyl isocyanate) cyclohexane, and isophorone diisocyanate.

Caprolactone-modified (meth)acrylate is a compound that can be obtained by addition polymerizing ε-caprolactone to (meth)acrylate or hydroxy group-containing (meth)acrylate. Hydroxyl group-containing (meth)acrylate is a compound having a (meth)acryloyl group and a hydroxy group. (meth)acryloyl group is a concept including methacryloyl group and acryloyl group, and means methacryloyl group or acryloyl group.

Examples of hydroxy group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates. Specific examples of hydroxyalkyl (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. Examples include 2-hydroxybutyl, 3-hydroxybutyl (meth)acrylic acid, 4-hydroxybutyl (meth)acrylic acid, 6-hydroxyhexyl (meth)acrylic acid, and 8-hydroxyoctyl (meth)acrylic acid. .

Examples of commercially available caprolactone-modified (meth)acrylates include Fraxel FA1, Fraxel FA2D, and Fraxel FA5 (trade name, manufactured by Daicel Kagaku Kogyo).

(M1) Component may be used individually by 1 type, or 2 or more types may be used together.

The ratio of the (M1) component in the (M) component is, for example, preferably 40 to 100% by mass, more preferably 50 to 95% by mass, relative to the total amount (100% by mass) of the (M) component, 70 to 90 mass% is more preferable, and 75 to 85 mass% is particularly preferable. Alternatively, the ratio of the (M1) component in the (M) component is, for example, preferably 40 to 100 mol%, and more preferably 50 to 95 mol%, relative to the total amount (100 mol%) of the (M) component. And, 70 to 90 mol% is more preferable, and 75 to 85 mol% is particularly preferable. By keeping the ratio of the (M1) component in the (M) component within the above preferred range, the occurrence of delamination in a high temperature process can be suppressed while maintaining cleanability.

≪Other crosslinking agent components: (M2) component≫

In addition to the (M1) component, the (M) component may include another crosslinking agent component (hereinafter also referred to as the "(M2) component"). Examples of the (M2) component include compounds having two or more (meth)acryloyl groups (excluding the component (M1) above). Examples of the (M2) component include polyfunctional urethane (meth)acrylate, polyfunctional (meth)acrylate, and polyfunctional caprolactone-modified (meth)acrylate. When the adhesive composition of this embodiment contains the (M2) component, the (P1) component corresponding to the (M2) component is excluded.

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

[In the formula, Ry ¹ to Ry ³ each independently represent a group represented by -O-(CH ₂ ) _k -OCOCH=CH ₂ (k is an integer of 1 to 10). Rm ¹ to Rm ⁷ are the same as Rm ¹ to Rm ⁷ in the above formulas (m1-1) to (m1-3).]

Preferred specific examples of polyfunctional urethane (meth)acrylate are shown below, but are not limited to these.

[In the formula, Ry ¹¹ to Ry ¹³ represent a group represented by -O-(CH ₂ ) ₂ -OCOCH=CH _2. ]

A (meth)acrylate compound is a compound containing a (meth)acryloyl group. Examples of the (meth)acrylate compound as the (M2) component include those similar to the (O1) component.

Examples of multifunctional (meth)acrylates include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl. Bifunctional (meth)acrylates such as glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and ethoxylated bisphenol A diacrylate; Trifunctional (meth)acrylates such as trimethylolpropane triacrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. You can.

Examples of the polyfunctional caprolactone-modified (meth)acrylate include caprolactone-modified ((meth)acrylate alkyl) isocyanurate, such as caprolactone-modified tris (2-(meth)acryloxyethyl) isocyanurate. You can.

(M2) Component may be used individually by 1 type, or 2 or more types may be used together.

The ratio of the (M2) component in the (M) component is, for example, preferably 0 to 60% by mass, more preferably 5 to 50% by mass, relative to the total amount (100% by mass) of the (M) component. 10 to 40 mass% is more preferable, and 10 to 30 mass% is particularly preferable. Alternatively, the ratio of the (M2) component in the (M) component is preferably 0 to 60 mol%, more preferably 5 to 50 mol%, and 10 to 10 mol%. 40 mol% is more preferable, and 10 to 30 mol% is particularly preferable.

When the (M) component contains the (M2) component, the molar ratio of the (M1) component and the (M2) component ((M1) component:(M2) component) is, for example, 99:1 to 20:80. can be mentioned. The molar ratio of component (M1) and component (M2) is preferably 95:5 to 30:70, more preferably 90:10 to 40:60, further preferably 90:10 to 50:50, and 90: 10~60:40 is particularly preferable.

The ratio of component (M) in the adhesive composition of this embodiment is, for example, preferably 10 to 60% by mass, more preferably 10 to 50% by mass, with respect to the total mass (100% by mass) of the adhesive composition. , 20 to 40 mass% is more preferable, and 25 to 35 mass% is particularly preferable.

The mass ratio ((P1) component:(M) component) of the component (P1) and the component (M) is preferably 95:5 to 50:50, more preferably 90:10 to 60:40, and 80:50. 20~60:40 is more preferable.

<Polymerization initiator: (A) component>

The adhesive composition of this embodiment contains, in addition to the above-mentioned (P1) component and (M) component, a polymerization initiator (hereinafter also referred to as (A) component). A polymerization initiator refers to a component that has the function of promoting a polymerization reaction. (A) As a component, a thermal polymerization initiator, a photo polymerization initiator, etc. are mentioned.

Examples of thermal polymerization initiators include peroxides and azo-based polymerization initiators.

Examples of peroxides in the thermal polymerization initiator include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, and peroxy ester. Specifically, such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, and 4-chlorobenzoyl peroxide. Chlorobenzoyl, 2,4-dichlorobenzoyl peroxide, 4-bromomethyl benzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl-2-methyl propyl- 1-hydroperoxide, tert-butyl pertriphenyl acetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, and-4 -Methoxy acetic acid tert-butyl, per-N-(3-tolyl)carbamic acid tert-butyl, etc.

The above peroxides include, for example, those manufactured by Nippon Yushi Co., Ltd. under the brand name “Percumil (registered trademark),” “Perbutyl (registered trademark),” “Peroil (registered trademark),” and “Perocta.” (registered trademark)” and other commercially available products can be used.

Examples of the azo-based polymerization initiator in the thermal polymerization initiator include 2,2'-azo bispropane, 2,2'-dichloro-2,2'-azo bispropane, and 1,1'-azo (methyl ethyl ) Diacetate, 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis(2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'- Azobisisobutyl amide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methyl methyl propionate, 2,2'-dichloro-2,2'-azobisbutane, 2, 2'-azobis-2-methylbutyronitrile, 2,2'-azo dimethyl bisisobutyrate, 1,1'-azobis(sodium 1-methylbutyronitrile 3-sulfonate), 2-(4- Methylphenylazo)-2-methylmalonodinitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis- 2-methylvaleronitrile, 4,4'-azobis-4-cyanovalerate dimethyl, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile , 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis- 1-chlorophenyl ethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1, 1'-azobiscumene, 4-nitrophenylazobenzylcyano ethyl acetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1, Examples include 2-diphenyl ethane, poly(bisphenol A-4,4'-azobis-4-cyanopentanoate), and poly(tetraethylene glycol-2,2'-azobis isobutyrate). .

Examples of photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl. ]-2-Hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl propan-1-one, 1-(4-dodecyl Phenyl)-2-hydroxy-2-methyl propan-1-one, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl- 1-[4-(methylthio) phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl amino-1-(4-morpholinophenyl)-butan-1-one, ethane On-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethyl benzoyl diphenyl phosphine oxide , 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid. , 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o- Methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthone Oxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3 -Diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o- Chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)- 4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl Imidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e. Michler's ketone), 4,4' -Bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoinmethyl 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, p-t-butylacetophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, α,α-dichloro- 4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 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- 1) Ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s -Triazine, 2-[2-(4-diethylamino-2-methyl phenyl) 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-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2 -Bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl s-triazine, 2,4 -Bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, etc. are mentioned.

The above photopolymerization initiators include, for example, “IRGACURE OXE02”, “IRGACURE OXE01”, “IRGACURE 369”, “IRGACURE 651”, “IRGACURE 907” (all brand names, manufactured by BASF) and “NCI-831” ( Commercially available products such as those under the brand name (ADEKA, Inc.) can be used.

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

<Arbitrary component>

The adhesive composition of this embodiment may contain, in addition to the above-mentioned (P1) component, (M) component, and (A) component, an arbitrary component within the range that does not impair the effect of the present invention. The optional components are not particularly limited, but examples include polymerization inhibitors, solvent components, plasticizers, adhesion aids, stabilizers, colorants, and surfactants.

≪Polymerization inhibitor≫

A polymerization inhibitor refers to a component that has the function of preventing radical polymerization reaction caused by heat or light. Polymerization inhibitors exhibit high reactivity to radicals.

As a polymerization inhibitor, one having a phenol skeleton is preferable. For example, as such polymerization inhibitors, it is possible to use hindered phenol-based antioxidants, such as pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butyl catechol, monobenzyl ether, methyl hydroquinone, and amylquinone. , amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene) bis(2-methylphenol), 4,4'-(1-methylethylidene) ) Bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4,4', 4"-ethylidene tris(2-methylphenol), 4,4',4"-ethylidene trisphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenyl Propane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylene bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene bis(3-methyl -6-tert-butylphenol), 4,4'-thio bis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert-butyl-4-hyde Roxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, triethylene glycol-bis-3-(3- tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythril tetrakis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (brand name IRGANOX 1010, manufactured by BASF), tris(3,5-di-tert-butylhydroxybenzyl) isosylate Anurate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], etc. are mentioned.

The polymerization inhibitor may be used individually by one type, or may be used in combination of two or more types.

The content of the polymerization inhibitor may be appropriately determined depending on the type of resin component, the purpose of the adhesive composition, and the usage environment.

≪Surfactant≫

Examples of surfactants include fluorine-based surfactants and silicone-based surfactants.

As fluorine-based surfactants, for example, BM-1000, BM-1100 (all manufactured by BM Chemistry), Megapack F142D, Megapack F172, Megapack F173, Megapack F183 (all manufactured by DIC), Florad FC- 135, Florad FC-170 C, Florad FC-430, Florad FC-431 (all made by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S- 141, use commercially available fluorine-based surfactants such as Surfron S-145 (all manufactured by Asahi Glass), SH-28 PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone). I can hear it.

Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants. You can. A commercially available silicone surfactant can be used. Specific examples of commercially available silicone-based surfactants include, for example, Painted M (manufactured by Toray Dow Corning), Topeka K1000, Topeka K2000, Topeka K5000 (all made by Takachiho Sankyo), and XL-121 (polyether-modified silicone-based interface). Activator, manufactured by Kurariant Corporation), BYK-310 (polyester modified silicone-based surfactant, manufactured by Big Chemistry Corporation), etc. are mentioned.

Surfactant may be used individually by 1 type, or may be used in combination of 2 or more types. As the surfactant, silicone-based surfactants are preferable, and polyester-modified silicone-based surfactants are more preferable. When using a surfactant, the content of the surfactant in the adhesive composition of this embodiment is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass, based on 100 parts by mass of component (P1).

≪Solvent ingredients≫

The adhesive composition of this embodiment can be prepared by dissolving and mixing the (P1) component, (M) component, and (A) component, and optional components in a solvent component as needed. As a solvent component, a solvent capable of dissolving each of the above components can be used.

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

Examples of hydrocarbon solvents include linear, branched, or cyclic hydrocarbons. Examples of hydrocarbon solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; Branched chain hydrocarbons such as isooctane, isononane, and isododecane; p-Menthane, o-Menthane, m-Menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinan, tuzan, caran, longipolene, α-terpinene , alicyclic hydrocarbons such as β-terpinene, γ-terpinene, α-pinene, β-pinene, α-tuyon, β-tuyon, cyclohexane, cycloheptane, and cyclooctane; Aromatic hydrocarbons such as toluene, xylene, indene, pentalene, indane, tetrahydroindane, naphthalene, tetrahydronaphthalene (tetraline), and decahydronaphthalene (decalin) can be mentioned.

A petroleum-based solvent is a solvent purified from heavy oil, and examples include white kerosene, paraffin-based solvent, and isoparaffin-based solvent.

(S2) Components include terpene solvents having an oxygen atom, carbonyl group, or acetoxy group as a polar group, for example, geraniol, nerol, linalool, citral, citronerol, menthol, iso Menthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinel acetate, 1,4-cineol, Examples include 1,8-cineole, borneol, carvone, ionone, thuyon, and campol.

Additionally, the (S2) component includes lactones such as γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ether, monoethyl ether of the above polyhydric alcohols or compounds having the above ester bond, Derivatives of polyhydric alcohols, such as monoalkyl ethers such as monopropyl ether and monobutyl ether, or compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); Cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, and butylphenyl ether can also be mentioned.

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

The content of the solvent component in the adhesive composition of this embodiment may be adjusted appropriately according to the thickness of the adhesive composition layer. The content of the solvent component is preferably within the range of 40 to 90% by mass, for example, based on the total amount (100% by mass) of the adhesive composition. That is, the adhesive composition of this embodiment preferably has a solid content (total amount of compounding components excluding solvent components) concentration within the range of 10 to 80 mass%. If the content of the solvent component is within the above preferred range, viscosity adjustment becomes easy.

The polymerization initiator can be mixed by a known method immediately before using the adhesive composition. The polymerization initiator or polymerization inhibitor may be mixed in the form of a solution previously dissolved in the component (S2). The amount of the component (S2) used may be adjusted appropriately depending on the type of polymerization initiator or polymerization inhibitor, etc., for example, preferably 1 to 50 parts by mass, and 5 to 30 parts by mass per 100 parts by mass of the (S1) component. It is more desirable. (S2) If the amount of component used is within the above preferred range, the polymerization initiator or polymerization inhibitor can be sufficiently dissolved.

According to the adhesive composition according to the present embodiment, since it contains a urethane resin (P1) containing a polymerizable carbon-carbon double bond, caprolactone-modified urethane acrylate (M1), and a polymerization initiator (A), When the polymerization reaction is initiated, the (P1) component and the (M1) component polymerize to form a crosslinked structure and harden. Since the adhesive layer formed by curing such an adhesive composition is cured through a crosslinked structure, it has high heat resistance and does not lower its elastic modulus even at high temperatures (for example, 200°C or higher). Additionally, the adhesive layer has flexibility due to the ring-opened caprolactone structure in the component (M1), and has high adhesion to the substrate. Therefore, after performing temporary adhesion between the semiconductor substrate and the like and the support, the electronic device formation process can be performed satisfactorily.

On the other hand, the urethane bond in component (P1) can be decomposed by acid or alkali. Therefore, after the electronic device formation process or the like is completed, the adhesive layer attached to the electronic device can be easily cleaned and removed. Additionally, when the adhesive composition contains component (M1), cleanability is also improved.

(Laminate)

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 electronic device are laminated in this order, and the adhesive layer is a cured product of the adhesive composition according to the first aspect. Do it as

Fig. 1 shows one embodiment of a laminate according to the second aspect.

The laminate 100 shown in FIG. 1 includes a support 12 in which a support base 1 and a separation layer 2 are laminated, an adhesive layer 3, and a semiconductor substrate 4. In the laminate 100, the support 12, the adhesive layer 3, and the semiconductor substrate 4 are stacked in this order.

In the example of FIG. 1, the support body 12 is comprised of the support base 1 and the separation layer 2, but it is not limited to this, and the support may be comprised only of the support base.

Figure 2 shows another embodiment of a laminate according to the second aspect.

The laminate 200 shown in FIG. 2 is a laminate except that an electronic device 456 consisting of a semiconductor substrate 4, an encapsulating material layer 5, and a wiring layer 6 is laminated on an adhesive layer 3. It has the same configuration as (100).

Fig. 3 shows another new embodiment of the laminate according to the second aspect.

The laminate 300 shown in FIG. 3 has the same structure as the laminate 100 except that the electronic device is made of a wiring layer 6.

Fig. 4 shows another new embodiment of the laminate according to the second aspect.

The laminate 400 shown in FIG. 4 is a laminate except that an electronic device 645 consisting of a wiring layer 6, a semiconductor substrate 4, and an encapsulating material layer 5 is laminated on the adhesive layer 3. It has the same configuration as (100).

<Support>

A support body is a member that supports a semiconductor substrate or electronic device. In the examples of FIGS. 1 to 4 , the support body 12 includes a support base 1 and a separation layer 2 provided on the support base 1. In the laminate of this embodiment, the support may or may not have the separation layer 2. If the support does not have the separation layer 2, the support substrate 1 becomes the support.

≪Support body≫

The support base is a member that has the characteristic of transmitting light and supports the semiconductor substrate or electronic component. When a separation layer is provided as shown in FIGS. 1 to 4, the support base is bonded to the semiconductor substrate or electronic device through the separation layer and the adhesive layer. In the case where the separation layer is not provided, the support base is bonded to the semiconductor substrate or electronic device through an adhesive layer. Therefore, the support base preferably has the necessary strength to prevent damage or deformation of the semiconductor substrate during thinning of the device, transportation of the semiconductor substrate, mounting on the semiconductor substrate, etc. In addition, when the support has a separation layer, it is preferable that the support substrate transmits light of a wavelength that can deteriorate the separation layer.

As materials for the support base, for example, glass, silicone, acrylic resin, etc. are used. The shape of the support base includes, for example, a rectangular shape, a circular shape, etc., but is not limited to these. As the support base, for new high-density integration and improved production efficiency, a larger circular support base can be used, or a large panel with a rectangular shape in plan view can be used.

≪Separation layer≫

The separation layer is adjacent to the adhesive layer and is a layer that deteriorates by irradiation of light and makes it possible to separate the support substrate from the semiconductor substrate or electronic device fixed to the support through the adhesive layer.

This separation layer can be formed using a composition for forming a separation layer, which will be described later, and is formed, for example, by baking the components contained in the composition for forming a separation layer, or by a chemical vapor deposition (CVD) method. do. This separation layer is suitably altered by absorbing light irradiated through the support gas.

The separation layer is preferably formed from only a material that absorbs light, but may be a layer mixed with a material that does not have a light-absorbing structure, as long as the essential characteristics of the present invention are not impaired.

The thickness of the separation layer is preferably, for example, within the range of 0.05 μm or more and 50 μm or less, and more preferably within the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, desired deterioration in the separation layer can be caused by irradiation of light for a short period of time or irradiation with low energy light. In addition, it is particularly preferable that the thickness of the separation layer is within the range of 1 μm or less from the viewpoint of productivity.

It is preferable that the surface of the separation layer in contact with the adhesive layer is flat (no convexities and protrusions are formed), so that the formation of the adhesive layer can be easily performed, and further, a semiconductor substrate or electronic device, It becomes easy to uniformly adhere the support base.

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 containing a light-absorbing structure, an inorganic material, a compound having an infrared-absorbing structure, and an infrared-absorbing structure. Examples include those containing a substance, reactive polysilsesquioxane, or a resin component having a phenol skeleton.

In addition, the composition for forming a separation layer may include, as optional components, a filler, a plasticizer, a thermal acid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a component that can improve the separation of the support gas. etc. may be included.

··Fluorocarbon

The separation layer may contain fluorocarbon. The separation layer made of fluorocarbon deteriorates by absorbing light, and as a result, it loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a small external force (for example, lifting the support), the separation layer is destroyed, and the support and the semiconductor substrate or electronic device can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed into a film by the plasma CVD method.

Fluorocarbon absorbs light with a unique range of wavelengths depending on its type. By irradiating the separation layer with light of a wavelength within the range absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably modified. The light absorption rate of the separation layer is preferably 80% or more.

The light irradiated to the separation layer depends on the wavelength that the fluorocarbon can absorb, for example, solid lasers such as YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber laser, and liquid lasers such as dye laser. Laser light such as a laser, a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, a He-Ne laser, a semiconductor laser, a free electron laser, or non-laser light may be appropriately used. As a wavelength that can deteriorate fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

··Polymer having a repeating unit containing a light-absorbing structure

The separation layer may contain a polymer having a repeating unit containing a structure having light absorption properties. The polymer deteriorates when irradiated with light.

Examples of structures that have light absorption include an atomic group containing a conjugated π electron system made of a substituted or unsubstituted benzene ring, condensed ring, or heterocycle. The structure having light absorption is more specifically, a cardo structure, or a benzophenone structure, diphenyl sulfoxide structure, diphenyl sulfone structure (bisphenyl sulfone structure), diphenyl structure, or A diphenyl amine structure may be mentioned.

The structure having the above-mentioned light absorption property can absorb light having a wavelength in a desired range, depending on its type. For example, the wavelength of light that can be absorbed by the structure having the light absorbing property described above is preferably within the range of 100 to 2000 nm, and more preferably within the range of 100 to 500 nm.

Light that can be absorbed by the structure having the above light absorption properties includes, for example, a high-pressure mercury lamp (wavelength 254 nm or more, 436 nm or less), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), Light emitted from an F ₂ excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), (wavelength 405 nm) or i-line (wavelength 365 nm).

··Inorganic matter

The separation layer may be made of an inorganic material. This inorganic material may be any material that changes by absorbing light, and suitable examples include one or more types selected from the group consisting of metals, metal compounds, and carbon. A metal compound is a compound containing a metal atom, and examples include metal oxide and metal nitride.

Examples of such inorganic materials include one or more types selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon.

Additionally, carbon is a concept that can also include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, and carbon nanotubes.

The inorganic material absorbs light having a unique range of wavelengths depending on its type.

As light irradiated to the separation layer made of an inorganic material, depending on the wavelength that the inorganic material can absorb, for example, solid lasers such as YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber laser, dye laser, etc. Liquid 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.

The separation layer made of an inorganic material can be formed on the support base by, for example, known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

··Compound having an infrared absorbing structure

The separation layer may contain a compound having an infrared absorbing structure. This compound having an infrared absorbing structure deteriorates by absorbing infrared rays.

Examples of structures with infrared absorption or compounds having this structure include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, cyclic), and alkynes (monosubstituted). , 2-substituted), monocyclic aromatic (benzene, 1-substituted, 2-substituted, 3-substituted), alcohol or phenol (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated secondary, saturated tertiary, unsaturated secondary grade, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, enol of 1,3-diketone, o -Hydroxyaryl ketone, dialkyl aldehyde, 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 chlorides, aromatic acid chlorides, acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, primary amines (aliphatic, aromatic), secondary amines (aliphatic, aromatic) ), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile Nitrile, isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitro amine, nitrosamine, nitric acid ester, nitrous acid ester, nitroso bond (aliphatic, aromatic, monomer, dimer), sulfur compounds such as mercaptan or thiophenol or thiolic acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfuric acid ester , carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² bond (A ² is H, C or O), or Ti-O bond.

Structures containing the above carbon-halogen bond include, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , aryl fluoride, or aryl chloride.

Structures containing the above Si-A ¹ bond include, 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 , etc. As a structure containing a Si-A ¹ bond, one forming a siloxane skeleton or silsesquioxane skeleton is particularly preferable.

Structures containing the above PA ² bond include, for example, PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is an aliphatic group or an aromatic group ), (A ⁴ O) ₃ -PO (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH or O=P-OH, etc. You can.

Examples of compounds containing the above Ti-O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, or titanium-i -Alkoxy titanium such as propoxy octylene glycolate; (ii) chelated titanium such as di-i-propoxy·bis(acetylacetonate) titanium or propanedioxytitanium bis(ethylacetoacetate); (iii) iC ₃ H ₇ O-[-Ti(OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ or nC ₄ H ₉ O-[-Ti(OnC ₄ H ₉ ) ₂ -O-] titanium polymers such as _n -nC ₄ H ₉ ; (iv) Acrylates such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, or (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium. titanium; (v) water-soluble titanium compounds such as di-n-butoxy·bis(triethanolaminate) titanium; and the like.

Among these, compounds containing a Ti-O bond include di-n-butoxy·bis(triethanolaminate) titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH) ₂ ] ₂ ) is preferable.

The above infrared absorbing structure can absorb infrared rays having a wavelength in a desired range depending on the type selected. Specifically, the wavelength of infrared rays that can be absorbed by the above-mentioned infrared absorbing structure is, for example, within the range of 1 to 20 μm, and can more suitably absorb within the range of 2 to 15 μm.

Additionally, when the structure is a Si-O bond, Si-C bond, or Ti-O bond, the range is preferably within the range of 9 to 11 μm.

Additionally, the wavelength of infrared rays that can be absorbed by each of the above structures can be easily understood by those skilled in the art. For example, as an absorption band in each structure, non-patent literature: SILVERSTEIN, BASSLER, and MORRILL, “Spectral identification of organic compounds (5th edition) - Combination use of MS, IR, NMR, and UV - 」(published in 1992) You can refer to the descriptions on pages 146 to 151.

The compound having an infrared absorbing structure used to form the separation layer is a compound having the above-mentioned structure, and is specifically limited as long as it can be dissolved in a solvent for application and solidified to form a high layer. That is not the case. However, in order to effectively modify the compound in the separation layer and facilitate separation of the support base and the substrate, the absorption of infrared rays in the separation layer must be large, that is, the infrared transmittance when infrared rays are irradiated to the separation layer. This low value is desirable. Specifically, it is preferable that the infrared transmittance in the separation layer is lower than 90%, and it is more preferable that the infrared transmittance is lower than 80%.

··Infrared absorbing material

The separation layer may contain an infrared absorbing material. This infrared absorbing material can be any material that deteriorates by absorbing light, and for example, carbon black, iron particles, or aluminum particles can be suitably used.

Infrared absorbing materials absorb light with a unique range of wavelengths depending on their type. By irradiating the separation layer with light of a wavelength within the range absorbed by the infrared absorption material used in the separation layer, the infrared absorption material can be appropriately modified.

··Reactive polysilsesquioxane

The separation layer can be formed by polymerizing reactive polysilsesquioxane. The separation layer formed by this 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 that can form a silanol group by hydrolysis. They can be polymerized with each other by condensing the silanol group or the functional group capable of forming a silanol group. In addition, if the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, it has a silsesquioxane skeleton such as a random structure, a basket-like structure, or a ladder structure. Reactive polysilsesquioxane can be employed.

The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol%, and more preferably 80 to 99 mol%.

If the siloxane content of the reactive polysilsesquioxane is within the above preferred range, a separation layer that can be suitably modified by irradiation with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9 to 11 μm) can be formed. can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, and more preferably 1,000 to 10,000.

If the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above preferred range, it can be suitably dissolved in a solvent and suitably applied on a support plate.

Examples of commercial products that can be used as reactive polysilsesquioxane include SR-13, SR-21, SR-23, or SR-33 (brand name) manufactured by Konishi Chemical Corporation.

··Resin component having phenol skeleton

The separation layer may contain a resin component having a phenol skeleton. By having a phenol skeleton, it is easily deteriorated (oxidized, etc.) by heating, etc., and photoreactivity increases.

“Having a phenol skeleton” here means containing a hydroxybenzene structure.

The resin component having a phenol skeleton has film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1,000 to 30,000, more preferably 1,500 to 20,000, and particularly preferably 2,000 to 15,000. When the molecular weight of the resin component is below the upper limit of the above preferred range, the solubility of the composition for forming a separation layer in a solvent can be increased.

In addition, as the molecular weight of the resin component, the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography) is used.

Resin components having a phenol skeleton include, for example, novolak-type phenol resin, resol-type phenol resin, hydroxystyrene resin, hydroxyphenyl silsesquioxane resin, hydroxybenzyl silsesquioxane resin, and phenol skeleton-containing acrylic resin. etc. can be mentioned. Among these, novolak-type phenol resin and resorc-type phenol resin are more preferable.

<Adhesive layer>

The adhesive layer is provided to temporarily adhere the semiconductor substrate or electronic device to the support. The adhesive layer is a cured body of the adhesive composition according to the first embodiment. More specifically, the adhesive layer is formed by polymerizing and crosslinking the (P1) component and (M1) component in the adhesive composition according to the first embodiment above by polymerizable carbon-carbon double bonds. The polymerization reaction of component (P1) and component (M1) can be performed by heating the adhesive composition. The thickness of the adhesive layer is preferably, for example, 1 μm or more and 200 μm or less, and more preferably 5 μm or more and 150 μm or less.

As described above, the adhesive layer is a cured body of the adhesive composition. However, the material (cured body) constituting this adhesive layer preferably satisfies the following characteristics.

That is, when the complex elastic modulus of the cured body is measured under the following conditions, the complex elastic modulus at 200°C is preferably 1.0Х10 ⁶ Pa or more, more preferably 5.0Х10 ⁶ Pa or more, and even more preferably 1.0Х10 ⁷ Pa or more. desirable. The upper limit of the complex elastic modulus at 200°C is, for example, 1.0Х10 ¹⁰ Pa or less.

Additionally, when the complex elastic modulus of the cured body is measured under the following conditions, the complex elastic modulus at 250°C is preferably 5.0Х10 ⁶ Pa or more, and more preferably 1.0 Х10 ⁷ Pa or more. The upper limit of the complex elastic modulus at 250°C is, for example, 1.0Х10 ¹⁰ Pa or less.

The complex elastic modulus of the cured body can be measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Corporation). Specifically, the adhesive composition was applied on a PET film with a release agent, heated at 180°C for 1 hour in an oven under a nitrogen atmosphere to form a test piece with a thickness of 50 μm, and then peeled off from the PET film (size 5 mmХ40 mm, thickness 50 μm) can be measured using the above-mentioned measuring device. The measurement conditions may be tensile conditions with a frequency of 1 Hz and a temperature increase from an initial temperature of 50°C to 300°C at a temperature increase rate of 5°C/min.

<Semiconductor substrate or electronic device>

The semiconductor substrate or electronic device is temporarily bonded to the support through an adhesive layer.

≪Semiconductor substrate≫

There is no particular limitation on the semiconductor substrate, and examples thereof include those similar to those exemplified in “(Adhesive Composition)” above. The semiconductor substrate may be a semiconductor element or another element, and may have a single-layer or multi-layer structure.

≪Electronic device≫

There is no particular limitation on the electronic device, and examples thereof include those similar to those exemplified in “(Adhesive Composition)” above. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. Specifically, the electronic device may include at least one of an encapsulating material layer and a wiring layer, and may further include a semiconductor substrate.

In the laminate 200 shown in FIG. 2, the electronic device 456 is comprised of a semiconductor substrate 4, an encapsulating material layer 5, and a wiring layer 6. In the laminate 300 shown in FIG. 3 , the electronic device 6 is comprised of a wiring layer 6 . In the laminate 400 shown in FIG. 4 , the electronic device 645 is comprised of a wiring layer 6, a semiconductor substrate 4, and an encapsulating material layer 5.

[Encapsulation material layer]

The sealing material layer is provided to seal the semiconductor substrate, and is formed using a sealing material. As the sealing material, a member capable of insulating or sealing a member made of metal or semiconductor is used.

As a sealing material, for example, a resin composition can be used. It is preferable that the encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but is provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3. The resin used for the sealing material is not particularly limited as long as it can seal and/or insulate a metal or semiconductor, but examples include epoxy resin or silicone resin.

The encapsulating material may contain other components such as fillers in addition to the resin. Examples of fillers include spherical silica particles.

≪Wiring layer≫

The wiring layer, also called RDL (Redistribution Layer), is a thin film wiring body that constitutes wiring connected to the substrate, and may have a single-layer or multi-layer structure. The wiring layer is a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold and silver, and silver-tin alloy) between a dielectric (photosensitive resin such as silicon oxide (SiO _x ), photosensitive epoxy, etc.). The wiring may be formed by an alloy of, but is not limited to this.

In addition, in the laminate of FIGS. 1 to 4, the support base 1 and the separation layer 2 are adjacent to each other, but this is not limited to this, and another layer is present between the support base 1 and the separation layer 2. This addition may be formed. 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 provides desirable properties, etc. to the laminates 100 to 400 without interfering with the incidence of light into the separation layer 2. Depending on the type of material constituting the separation layer 2, the wavelength of light that can be used is different. Accordingly, the materials constituting the other layers do not need to transmit light of all wavelengths, but can be appropriately selected from materials that transmit light of a wavelength that may deteriorate the material constituting the separation layer 2.

(Method for manufacturing laminate (1))

The method for manufacturing a laminate according to the third aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, wherein the adhesive composition according to the first aspect is applied to the support or the semiconductor substrate. A process of applying an adhesive composition layer (hereinafter also referred to as “adhesive composition layer forming process”), and a process of placing the semiconductor substrate on the support through the adhesive composition layer (hereinafter referred to as “semiconductor substrate”) It is characterized by having a step of curing the adhesive composition layer through a polymerization reaction of the urethane resin to form the adhesive layer (hereinafter also referred to as the “adhesive layer forming step”).

5 to 6 are schematic process diagrams explaining one embodiment of the method for manufacturing a laminated body according to the present embodiment.

5(a) to 5(c) are diagrams illustrating the manufacturing process of the laminate 100' in which the support 1, the adhesive composition layer 3', and the semiconductor substrate 4 are laminated in this order. . FIG. 5(a) is a diagram showing the support body 12. The support body 12 is composed of a support base 1 and a separation layer 2. FIG. 5(b) is a diagram explaining the adhesive composition layer forming process. Fig. 5(c) is a diagram explaining the semiconductor substrate mounting process.

Figure 6 is a diagram explaining the adhesive layer forming process. The adhesive composition layer 3' in the laminate 100' is thermoset to form the adhesive layer 3, and the laminate 100 is obtained.

[Adhesive composition layer formation process]

The method for manufacturing a laminate according to this embodiment includes an adhesive composition layer forming step. The adhesive composition layer forming process is a process of forming an adhesive composition layer by applying an adhesive composition to a support or semiconductor substrate. When the support has a separation layer, the adhesive composition layer is formed on the side of the support having the separation layer.

In Fig. 5(b), an adhesive composition layer 3' is formed on the surface of the support 12 on the side of the separation layer 2 using an adhesive composition.

The method of forming the adhesive composition layer 3' on the support 12 is not particularly limited, but examples include spin coating, dipping, roller blade, spray coating, and slit coating.

The adhesive composition layer may be formed on the semiconductor substrate 4 by a similar method.

After forming the adhesive composition layer, a bake treatment may be performed. The bake temperature condition is set to a temperature lower than the heating temperature in the adhesive layer forming process described later. Bake conditions may vary depending on the type of component (P1) contained in the adhesive composition, but examples include 1 to 10 minutes under temperature conditions of 70 to 100°C.

[Semiconductor substrate placement process]

The method for manufacturing a laminate according to this embodiment includes a semiconductor substrate placing process. The semiconductor substrate placing process is a process of placing a semiconductor substrate on a support through an adhesive composition layer. As a result, the laminate 100' can be obtained.

In FIG. 5(c), the semiconductor substrate 4 is placed on the support 12 through the adhesive composition layer 3' formed on the support 12.

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

[Adhesive layer formation process]

The manufacturing method of the laminated body according to this embodiment includes an adhesive layer forming process. The adhesive layer forming process is a process of curing the adhesive composition layer to form an adhesive layer. As a result, the laminate 100 can be obtained.

In Fig. 6, the adhesive layer 3 is formed by curing the adhesive composition layer 3'.

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

Examples of the heating temperature include 80 to 350°C, 100 to 300°C, 130 to 300°C, or 150 to 300°C.

The heating time is not particularly limited as long as it is sufficient for the (P1) component and (M1) component to polymerize and harden. As a heating time, for example, 30 to 180 minutes is preferable, 45 to 120 minutes is more preferable, or 60 to 120 minutes is still more preferable. The curing reaction can be performed, for example, under a nitrogen atmosphere.

According to this process chart, the (P1) component and the (M1) component in the adhesive composition layer 3' are crosslinked and cured, and the adhesive layer 3, which is a cured product of the adhesive composition layer 3', is formed. As a result, the support 12 and the semiconductor substrate 4 are temporarily bonded. As a result, the laminate 100 can be obtained.

[Random process]

The method for manufacturing a laminated body according to the present embodiment may include other processes in addition to the above processes. Other processes include, for example, a separation layer formation process and various mechanical or chemical treatments (thinning treatments such as grinding and chemical mechanical polishing (CMP), high temperature treatment such as chemical vapor deposition (CVD) and physical vapor deposition (PVD). · Treatment under vacuum, treatment using organic solvents, chemicals such as acid treatment liquid or basic treatment liquid, plating treatment, irradiation of actinic light, heating/cooling treatment, etc.).

·Separation layer formation process

When the support includes a separation layer, the method for manufacturing a laminate according to this embodiment may include a separation layer forming step. The separation layer forming process is a process of forming a separation layer on one side of the support base using a composition for forming a separation layer.

In FIG. 5(a), the separation layer 2 is formed on the support base 1 by using a composition for forming a separation layer (containing fluorocarbon) (i.e., the support base with a separation layer is being produced).

The method of forming the separation layer 2 on the support substrate 1 is not particularly limited, but includes, for example, spin coating, dipping, roller blade, spray coating, slit coating, chemical vapor deposition (CVD), etc. can be mentioned.

For example, in the separation layer formation process, the solvent component is removed from the coating layer of the composition for forming a separation layer applied on the support base 1 under a heating environment or a reduced pressure environment to form a film, or the support base 1 ), the support 12 can be obtained by forming a film on it by a vapor deposition method.

(Method for manufacturing laminate (2))

The method for manufacturing a laminate according to the fourth aspect of the present invention is to obtain a laminate by the method for manufacturing a laminate according to the third aspect, and then sealing the member with a member made of a metal or semiconductor, or It is characterized by additionally having an electronic device forming process to form an electronic device that is a composite with an insulating resin.

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

[Electronic device formation process]

The method for manufacturing a laminate according to this embodiment includes an electronic device forming process. The electronic device formation process is a process of forming an electronic device that is a composite of a member made of metal or a semiconductor and a resin that encapsulates or insulates the member.

The electronic device formation process may include any one of an encapsulation process, a grinding process, and a wiring layer formation process. In one embodiment, the electronic device forming process includes a substrate fixing process and an encapsulation process. In this case, the electronic device formation process may further include a grinding process and a wiring layer formation process.

·About the encapsulation process

The encapsulation process is a process of sealing the substrate fixed on the support using a sealing material.

In Fig. 7(a), a laminate 110 is obtained in which the entire semiconductor substrate 4 temporarily bonded to the support 12 through the adhesive layer 3 is sealed by the encapsulating material layer 5.

In the encapsulation process, for example, an encapsulant 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, and is compressed to form the adhesive layer. (3) A laminate 110 with the encapsulant layer 5 provided thereon is manufactured.

At that time, the temperature conditions are, for example, 130 to 170°C.

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

It is preferable that the encapsulant layer 5 is not provided for each individual semiconductor substrate 4, but is provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3.

·About the grinding process

The grinding process is a process of grinding the sealing material portion (sealing material layer 5) in the sealing body after the above-mentioned sealing process so that a part of the semiconductor substrate is exposed.

Grinding of the encapsulating material portion is performed by grinding the encapsulating material layer 5 until it has a thickness substantially equal to that of the semiconductor substrate 4, as shown in Fig. 7(b), for example.

·About the wiring layer formation process

The wiring layer forming process is a process of forming a wiring layer on the exposed semiconductor substrate after the grinding process.

In Fig. 7(c), a wiring layer 6 is formed on the semiconductor substrate 4 and the encapsulating material layer 5. As a result, the laminate 120 can be obtained. In the laminate 120, the semiconductor substrate 4, the encapsulant layer 5, and the wiring layer 6 constitute an electronic device 456.

As a method of forming the wiring layer 6, the following method can be mentioned, for example.

First, a dielectric layer such as silicon oxide (SiO _x ) or photosensitive resin is formed on the encapsulant layer 5 . The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method or a vacuum deposition method. The dielectric layer made of photosensitive resin can be formed by applying the photosensitive resin onto the encapsulant layer 5 by, for example, spin coating, dipping, roller blade, spray coating, or slit coating.

Next, wiring is formed in the dielectric layer using a conductor such as metal. As a method of forming the wiring, for example, known semiconductor process methods such as lithography processing such as photo lithography (resist lithography) and etching processing can be used. Examples of such lithography processing include lithography processing using a positive resist material and lithography processing using a negative resist material.

In the method for manufacturing a laminate according to the present embodiment, formation of bumps or mounting of elements can be additionally performed on the wiring layer 6. Mounting of elements on the wiring layer 6 can be performed using, for example, a tip mounter.

(Method for manufacturing laminate (3))

The method for producing a laminate according to the fifth aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order, wherein the adhesive composition according to the first aspect is applied on the support. A process of forming a layer of the adhesive composition by applying it (adhesive composition layer forming process), and an electronic device that is a composite of a member made of metal or a semiconductor and a resin that seals or insulates the member is placed on the adhesive composition layer. An electronic device forming step (electronic device forming step) and a step of curing the adhesive composition layer through a polymerization reaction of the urethane resin to form an adhesive layer (adhesive layer forming step).

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

In the manufacturing method of this embodiment, the adhesive composition layer forming process can be performed similarly to that in the manufacturing method of the laminate according to the third aspect.

In the manufacturing method of this embodiment, the electronic device forming process is performed after the adhesive composition layer forming process. This electronic device formation process may include a wiring layer formation process. The electronic device formation process may further include a semiconductor substrate placing process, an encapsulation process, a grinding process, etc. Additionally, the electronic device forming process may be a process of placing the semiconductor substrate encapsulated with an encapsulating material on a support through an adhesive composition layer.

The adhesive layer forming process can be performed similarly to that in the method for manufacturing a laminate according to the third aspect.

After the adhesive layer forming process, an electronic device forming process may be additionally performed as needed. This electronic device forming process may include, for example, a semiconductor substrate placing process, an encapsulation process, and a grinding process.

According to the method for manufacturing a laminate according to the third to fifth aspects, the support and the semiconductor substrate or electronic device are temporarily bonded through an adhesive layer with high heat resistance, so that the support, the adhesive layer, and the semiconductor substrate or electronic device are A laminate formed by stacking in this order can be stably manufactured. This laminate is a laminate manufactured in a process based on fan-out type technology in which terminals provided on a semiconductor substrate are mounted on a wiring layer that spreads beyond the chip area.

(Manufacturing method of electronic components)

The method for manufacturing an electronic component according to the sixth aspect of the present invention is to obtain a laminate by the method for manufacturing a laminate according to any one of the third to fifth aspects, and then combine the urethane bond of the urethane resin with an acid. Alternatively, it is characterized by having a step of removing the adhesive layer by decomposing it with an alkali (hereinafter also referred to as an “adhesive layer removal step”).

When the support is composed of a support base and a separation layer, the method according to the present embodiment irradiates light to the separation layer through the support base before the adhesive layer removal process, thereby deteriorating the separation layer. You may further include a separation step for separating the electronic device and the support substrate.

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

[Separation process]

When the support has a separation layer, the electronic component manufacturing method according to this embodiment may have a separation step. The separation process in the present embodiment irradiates light (arrow) to the separation layer 2 through the support base 1 to deteriorate the separation layer 2, thereby removing the support base from the electronic device 456. This is the process of separating (1).

As shown in FIG. 8(a), in the separation step, the separation layer 2 is deteriorated by irradiating light (arrow) to the separation layer 2 through the support base 1 that transmits light.

Examples of wavelengths that can cause deterioration of the separation layer 2 include a range of 600 nm or less.

The type and wavelength of light to be irradiated may be appropriately selected depending on the permeability of the support substrate 1 and the material of the separation layer 2, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, and LD laser. , solid-state lasers such as fiber lasers, liquid lasers such as dye lasers, gas lasers such as CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, laser lights such as semiconductor lasers, free electron lasers, and non-laser lights. You can. As a result, the separation layer 2 can be deteriorated so that the support base 1 and the electronic device 456 can be easily separated.

When irradiating a laser beam, the following conditions can be given as an example of the laser beam irradiation conditions.

The average output value of the laser light is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser light 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 light is preferably 100 mm/s or more and 10000 mm/s or less.

After irradiating light (arrow) to the separation layer 2 to deteriorate the separation layer 2, the support base 1 is separated from the electronic device 456, as shown in FIG. 8(b).

For example, the support body 1 and the electronic device 456 are separated by applying force in a direction in which the support body 1 and the electronic device 456 are separated from each other. Specifically, one side of the support base 1 or the electronic device 456 (wiring layer 6) is fixed to the stage, and the other side is held by suction using a separation plate provided with a suction pad such as a bellows pad. By lifting, the support base 1 and the electronic device 456 can be separated.

The force applied to the laminate 200 can be adjusted appropriately depending on the size of the laminate 200, etc., and is not limited. For example, if the laminate has a diameter of about 300 mm, the force is 0.1 to 5 kgf (0.98 to 0.98 kgf). By applying a force of about 49 N), the support body 1 and the electronic device 456 can be appropriately separated.

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

[Adhesive layer removal process]

The electronic component manufacturing method according to this embodiment has an adhesive layer removal process. The adhesive layer removal process is a process of decomposing the crosslinked structure in the adhesive layer with acid or alkali and removing the adhesive layer.

In Fig. 8(b), the adhesive layer 3 and the separation layer 2 are attached to the electronic device 456 after the separation process. In this process, the adhesive layer 3 and the separation layer 2 are decomposed using acid or alkali to remove the adhesive layer 3 and obtain the electronic component 50.

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

The above 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 include dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, propylene glycol, etc. You can.

In addition to the above components, the adhesive layer removal treatment liquid may contain known additives such as surfactants.

The acid or alkali content in the treatment liquid is not particularly limited, but examples include 1 to 50% by mass. Additionally, the content of the polar solvent in the treatment liquid may be 50 to 99% by mass.

The treatment liquid for removing the adhesive layer may be a commercially available alkaline treatment liquid or acidic treatment liquid. Examples of commercially available treatment liquids include ST-120 and ST-121 (all manufactured by Tokyo Ohka Kogyo).

By bringing the above treatment liquid containing acid or alkali into contact with the adhesive layer 3, the urethane bond of the (P1) component 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, an adhesive composition containing a urethane resin (P1) containing a polymerizable carbon-carbon double bond and a caprolactone-modified urethane acrylate (M1) is used to form a semiconductor substrate or The electronic device and the support are temporarily bonded. The adhesive layer formed by curing the adhesive composition is formed by a polymerization reaction of component (P1) and component (M1). By using an adhesive composition containing caprolactone-modified urethane acrylate (M1), an adhesive layer with high heat resistance and adhesion that can withstand high temperature treatment in an electronic device formation process, etc. can be formed. Additionally, since the urethane resin in the adhesive layer is decomposed by acid or alkali, the adhesive layer can be easily cleaned and removed after the electronic device formation process or the like is completed. Cleanability is also improved when the adhesive composition contains component (M1).

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

[Example]

Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples.

<Synthesis example of urethane resin>

(Synthesis Example 1: Urethane Resin (P1)-1)

In a flask equipped with a stirrer, dropping lot, cooling pipe, and thermometer, propylene glycol monomethyl ether acetate (PGMEA), 53 parts of polycarbonate diol (Mw 1000), 18 parts of pentaerythritol diacrylate (PEDA), and neopentyl glycol. 1 part and 2.5 parts of hydroxyethyl acrylate (HEA) were added and mixed uniformly under a nitrogen stream. Next, 7 parts of diphenyl methane diisocyanate (MDI) and 21 parts of hydrogenated xylene diisocyanate (H6XDI) were placed in the dropping funnel and added dropwise at a constant speed over 30 minutes. After completion of dropping, aging was performed for 30 minutes. After that, a bismuth catalyst was added, the temperature was raised to 65°C, and aging was performed for 4 to 5 hours. Next, methanol was added, aging was performed for 1 hour, and the reaction was terminated when the isocyanate group (NCO) disappeared. The molecular weight (Mw) of the obtained urethane resin (P1)-1 was 30,000.

The polycarbonate diol represented by the following formula (PC-1-1) was used (R=-(CH ₂ ) ₆ -, -(CH ₂ ) ₅ -).

<Preparation of adhesive composition>

(Examples 1-2, Comparative Examples 1-5)

The components shown in Table 1 were mixed to prepare adhesive compositions for each example.

In Table 1, each symbol has the following meaning. The numbers in [ ] are the mixing amount (parts by mass).

(P1)-1: Urethane resin (P1)-1 synthesized in Synthesis Example 1 above.

(M1)-1: A mixture of the following caprolactone-modified biuret-type urethane acrylate (M1-1) and the following biuret-type urethane acrylate (M2-1). By reacting caprolactone-modified hydroxyethyl acrylate and hydroxyethyl acrylate (caprolactone-modified hydroxyethyl acrylate:hydroxyethyl acrylate = 80:20 (molar ratio)) in a biuret sieve of hexamethylene diisocyanate. synthesized by.

(M1)-2: A mixture of the following caprolactone-modified isocyanurate type urethane acrylate (M1-2) and the following isocyanurate type urethane acrylate (M2-2). To the isocyanurate form of hexamethylene diisocyanate, caprolactone-modified hydroxyethyl acrylate and hydroxyethyl acrylate (caprolactone-modified hydroxyethyl acrylate:hydroxyethyl acrylate = 80:20 (molar ratio)) It was synthesized by reaction.

(M2)-1: The above-mentioned buret-type urethane acrylate (M2-1).

(M2)-2: The above isocyanurate type urethane acrylate (M2-2).

(M2)-3: Urethane acrylate (M2-3) below.

(M2)-4: Caprolactone-modified acrylate (M2-4) (Aronics M327 (brand name), Toagosei Kabushiki Kaisha Co., Ltd.) described below.

(A)-1: The following peroxide-based thermal polymerization initiator (A-1) (Percumil (registered trademark) D (brand name), Nippon Yushi Co., Ltd.).

(Ad)-1: The following silane coupling agent (Ad-1) (OFS-6040 Silane (brand name), Dow Toray Chemical Industry Co., Ltd.).

(Ad)-2: Polyester-modified polydimethyl siloxane (BYK-310 (brand name), BYK Chemistry).

The (M) component used in Examples 1, 2, and Comparative Examples 1 to 4 is summarized in Table 2.

<Evaluation>

≪Measurement of elastic modulus≫

Each adhesive composition was applied onto a silicon substrate using a 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 of the cured film of the adhesive composition (film thickness 50 μm, width 5 mm, length 40 mm) was cut, and the tensile elastic modulus was measured in the range of 50 to 300°C at a frequency of 1 Hz using Rheogel-E4000 (made by UBM). Measured.

≪Heat resistance test≫

On the silicon substrate, the adhesive composition of each example was applied by spin coating to form an adhesive composition layer (film thickness: 50 μm). Next, a glass support base (diameter 20 cm, thickness 700 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 and form an adhesive layer. The laminate consisting of this glass support base, adhesive layer, and silicon substrate was heated at 230°C in an oven under a nitrogen atmosphere, and the time until delamination occurred was measured. The results are shown in Table 3 as “delamination suppression time.”

≪Cleanability≫

Each adhesive composition was applied onto a silicon substrate using a spin coater method and heated at 180°C for 1 hour in an oven under a nitrogen atmosphere to form an adhesive layer. The silicon substrate of this adhesive layer former was immersed in an alkali-containing cleaning solution (ST-120 (brand name), manufactured by Tokyo Oka Kogyo Co., Ltd.) at 35°C or 50°C for 15 minutes, and the dissolution rate (nm/s) of the adhesive layer was measured. Measured. The results are shown in Table 3 as “cleanability.”

≪Adhesion≫

The adhesive compositions of each example were applied onto the silicon substrate using a spin coater method to form an adhesive composition layer (film thickness: 50 μm). Next, a glass chip (5 mmX5 mm, thickness 700 μm) including a separation layer 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 and form an adhesive layer. A shear strength test was performed on the laminate consisting of the glass chip, the adhesive layer, and the silicon substrate, and the shear strength of the glass chip with respect to the silicon substrate was measured. The results are shown in Table 3 as “adhesion.”

From the results shown in Table 3, it was confirmed that the adhesive layer formed using the adhesive composition of Examples 1 and 2 had good heat resistance (delamination suppression time), cleanability, and adhesion. On the other hand, Comparative Example 1 had excellent heat resistance, but cleanability was significantly poor. Comparative Example 2 had good heat resistance and adhesion, but was poor in cleanability. In Comparative Examples 3 and 4, heat resistance, cleanability, and adhesion were all inferior, and especially cleanability at low temperature (35°C) was significantly poor. Comparative Example 5 was inferior in heat resistance, cleanability, and adhesion.

1 Support gas
2 separation layer
3 adhesive layer
3' Adhesive composition layer
4 semiconductor substrate
5 Encapsulating material layer
6 wiring layer
12 support
20 Laminate
50 electronic components
100 laminate
100' laminate
110 laminate
120 laminate
200 laminate
300 laminate
400 laminate
456 electronic devices
645 electronic devices

Claims (10)

An adhesive composition used to form an adhesive layer that temporarily bonds a semiconductor substrate or electronic device and a light-transmitting support,
A urethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond,
caprolactone-modified urethane acrylate (M1),
Polymerization initiator (A)
Adhesive composition containing. In claim 1,
An adhesive composition wherein the caprolactone-modified urethane acrylate (M1) is a biuret type or an isocyanurate type. In claim 1,
An adhesive composition as the electronic device, wherein a composite of a member made of metal or a semiconductor and a resin that seals or insulates the member is laminated on the support through the adhesive layer. A laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device are laminated in this order,
The adhesive layer is a cured body of the adhesive composition of any one of claims 1 to 3,
Laminate. In claim 4,
The support is composed of a support base that transmits light and a separation layer that deteriorates by irradiation of light, and the adhesive layer is adjacent to the separation layer.
Laminate. A method of manufacturing a laminate in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, comprising:
A process of forming an adhesive composition layer by applying the adhesive composition of any one of claims 1 to 3 to the support or semiconductor substrate;
A step of placing the semiconductor substrate on the support through the adhesive composition layer;
Process of forming the adhesive layer by curing the adhesive composition layer
A method of manufacturing a laminate having a. After obtaining the laminate by the laminate manufacturing method of claim 6, there is further a step of forming an electronic device, which is a composite of a member made of metal or a semiconductor and a resin that encapsulates or insulates the member.
A method of manufacturing a laminate in which a support, an adhesive layer, and an electronic device are laminated in this order. In claim 7,
The support is composed of a support base that transmits light and a separation layer that deteriorates by irradiation of light, and in the laminate, the adhesive layer is adjacent to the separation layer,
Method for manufacturing a laminate. After obtaining a laminate by the method for manufacturing a laminate of claim 7,
Having a step of removing the adhesive layer by decomposing the urethane bond of the urethane resin with acid or alkali,
Manufacturing method of electronic components. After obtaining a laminate by the method for manufacturing a laminate of claim 8,
A process of separating the electronic device and the support base by irradiating light to the separation layer through the support base to alter the separation layer;
A process of removing the adhesive layer attached to the electronic device by decomposing the urethane bonds of the urethane resin with acid or alkali.
A manufacturing method of electronic components having a.