JP2020105276A - Adhesive composition, laminate, production method of laminate, and production method of electronic component - Google Patents

Abstract

To provide an adhesive composition which has high heat resistance and which facilitates removal of an adhesion layer, a laminate produced by using the adhesive composition, a production method of the laminate, and a production method of an electronic component using the adhesive composition.SOLUTION: An adhesive composition is used for forming an adhesion layer to temporarily bond a semiconductor substrate or an electronic device to a support medium, which conducts temporarily bonding by forming a crosslinking structure with heat and curing it, in which the crosslinking structure is decomposed with acid or alkali, and the adhesion layer is removed during a process of decomposition or after the process.SELECTED DRAWING: None

Description

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

There are various forms of semiconductor packages (electronic parts) including semiconductor elements according to the corresponding sizes, such as WLP (Wafer Level Package) and PLP (Panel Level Package).
Examples of semiconductor package technology include fan-in technology and fan-out technology. As a semiconductor package based on the fan-in type technology, a fan-in type WLP (Fan-in Wafer Level Package) in which terminals at the ends of bare chips are rearranged in a chip area is known. As a semiconductor package based on the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package) in which the terminals are rearranged outside the chip area is known.

In recent years, in particular, the fan-out type technology is applied to a fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged on a panel for packaging, and further higher integration in a semiconductor package, It has attracted attention as a method that can realize thinning and miniaturization.

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

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

International Publication No. 2016/52315

By the way, in manufacturing a semiconductor package, a high temperature treatment such as thin film formation, firing, and die bonding may be performed. If the heat resistance of the adhesive is low, there is a concern that the substrate may be displaced, the substrate may sink, or the like during high temperature processing. On the other hand, if the heat resistance of the adhesive is increased, the adhesiveness between the substrate and the support tends to decrease.
When a thermosetting adhesive is used to bond the support and substrate, problems such as misalignment and sinking do not occur during high temperature processing, but it is difficult to remove the adhesive layer with a solvent, etc. Even in such a case, it is difficult to remove the adhesive layer adhering to the substrate after separating the support and the substrate due to alteration of the separation layer.
The present invention has been made in view of the above circumstances, and is an adhesive composition having high heat resistance and capable of easily removing an adhesive layer, a laminate manufactured using the adhesive composition, and the laminate. It is an object of the present invention to provide a method for manufacturing the same and a method for manufacturing an electronic component using the adhesive composition.

In order to solve the above problems, the present invention adopts the following configurations.
That is, a first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support, wherein the adhesive composition is heated by heat. The temporary adhesion is performed by forming a crosslinked structure and curing, and the crosslinked structure is decomposed by an acid or an alkali, and the adhesive layer is removed during or after the decomposition process. It is an agent composition.

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

A third aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer and a semiconductor substrate are laminated in this order, and the adhesive composition according to the first aspect is added to the support or the semiconductor substrate. And an adhesive composition layer forming step of forming an adhesive composition layer by applying, and a semiconductor substrate placing step of placing the semiconductor substrate on the support through the adhesive composition layer. And a bonding layer forming step of forming a crosslinked structure in the adhesive composition layer by heating the adhesive composition layer to cure the adhesive composition layer, and forming an adhesive layer. is there.

A fourth aspect of the present invention is, after obtaining a laminated body by the method for producing a laminated body according to the third aspect, a member composed of a metal or a semiconductor, and a resin for sealing or insulating the member, Which is a composite of the above, further comprising an electronic device forming step of forming an electronic device, and is a method for producing a laminate in which a support, an adhesive layer and an electronic device are laminated in this order.

A 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 onto the support. And an electronic device which is a composite of an adhesive composition layer forming step of forming a layer of the adhesive composition, a member made of a metal or a semiconductor, and a resin for sealing or insulating the member. An electronic device forming step of forming the adhesive composition layer on the adhesive composition layer, and heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer and cure it to form an adhesive layer. And a step of forming an adhesive layer.

A sixth aspect of the present invention is to obtain a laminate by the method for producing a laminate according to any one of the third to fifth aspects, and then decompose the crosslinked structure in the adhesive layer with an acid or an alkali. A method of manufacturing an electronic component, comprising: an adhesive layer removing step of removing the adhesive layer.

A seventh aspect of the present invention is to obtain a laminate by the method for producing a laminate according to any one of the third to fifth aspects, and then irradiate the separation layer with light through the supporting substrate. , A separation step of separating the electronic device and the supporting substrate by modifying the separation layer, and after the separation step, the crosslinked structure in the adhesive layer is decomposed with an acid or an alkali, An adhesive layer removing step of removing the adhesive layer adhering to a device, the method of manufacturing an electronic component.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which has high heat resistance and whose adhesive layer is easy to remove, the laminated body manufactured using the said adhesive composition, the manufacturing method of the said laminated body, and this adhesive composition. A method of manufacturing an electronic component using a product is provided.

It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic process drawing explaining one Embodiment of the manufacturing method of laminated body 100' which laminated|stacked the support body, the adhesive composition layer, and the semiconductor substrate in this order. FIG. 5( a) is a diagram showing a support comprising a support base and a separation layer, FIG. 5( b) is a diagram for explaining the adhesive composition layer forming step, and FIG. 5( c) is It is a figure explaining a semiconductor substrate mounting process. It is a figure explaining an adhesive layer formation process. FIG. 6 is a schematic process diagram illustrating an embodiment of a method for manufacturing the laminated body 120. FIG. 7A is a diagram illustrating a sealing process, FIG. 7B is a diagram illustrating a grinding process, and FIG. 7C is a diagram illustrating a wiring layer forming process. FIG. 6 is a schematic process diagram illustrating an embodiment of a method of manufacturing a semiconductor package (electronic component) from the stacked body 120. FIG. 8A is a diagram showing the laminated body 200, FIG. 8B is a diagram illustrating a separation step, and FIG. 8C is a diagram illustrating an adhesive layer removal step. It is a graph which shows the behavior of the complex elastic modulus to the temperature of the hardening body of the adhesive composition to which the present invention is applied.

In the present specification and claims, the term “aliphatic” is defined as a concept relative to aromatic and means a group, compound or the like having no aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The “halogenated alkyl group” is a group in which a part or all of hydrogen atoms of an alkyl group are substituted with a halogen atom, and the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The “fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms.
The "structural unit" means a monomer unit (monomer unit) that constitutes a high molecular compound (resin, polymer, copolymer).
When describing that "may have a substituent" or "may have a substituent", a hydrogen atom (-H) may be substituted with a monovalent group and a methylene group (-CH ₂ Both the case where -) is substituted with a divalent group are included.
“Exposure” is a concept that includes all radiation irradiation.

The “structural unit derived from hydroxystyrene” means a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. The “structural unit derived from a hydroxystyrene derivative” means a structural unit formed by cleavage of the ethylenic double bond of the hydroxystyrene derivative.
The “hydroxystyrene derivative” is a concept including hydroxystyrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group and a halogenated alkyl group, and derivatives thereof. As the derivatives thereof, those obtained by substituting the hydrogen atom of the hydroxyl group of hydroxystyrene which may be substituted with a substituent with an organic group; and the hydrogen atom of the α-position may be substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group is bonded to the benzene ring of good hydroxystyrene. The α-position (carbon atom at the α-position) means the carbon atom to which the benzene ring is bonded, unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same ones as the substituents at the α-position in the above α-substituted acrylate ester.

The alkyl group as the α-position substituent is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
The halogenated alkyl group as the α-position substituent is specifically a group in which a part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent” is substituted with a halogen atom. To be Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as the α-position substituent include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent” are substituted with hydroxyl groups. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

In the present specification and claims, there are asymmetric carbons depending on the structures represented by the chemical formulas, and enantiomers (enantiomers) and diastereomers (diastereomers) may exist. In some cases, one formula represents these isomers. Those isomers may be used alone or as a mixture.

(Adhesive composition)
The adhesive composition according to the first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support, and the adhesive composition The object is to perform the temporary adhesion by forming a crosslinked structure by heat and curing, and the crosslinked structure is decomposed by an acid or alkali, and the adhesive layer is removed during or after the decomposition process. Is characterized in that

<Target of temporary adhesion>
The adhesive composition according to the present embodiment is used for forming an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support. In the present specification, “temporary adhesion” means that the objects to be adhered are temporarily adhered (for example, during an arbitrary work process). More specifically, the semiconductor substrate or the electronic device is temporarily adhered to the support and fixed on the support for the purpose of thinning the device, transporting the semiconductor substrate, mounting on the semiconductor substrate, etc. Adhesion), after the end of the process, it is separated from the support.

<<Semiconductor Substrate>>
The semiconductor substrate to which the adhesive composition according to the present embodiment is applied is not particularly limited, and may be one generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is subjected to processes such as thinning and mounting while being supported by a support. A structure such as an integrated circuit or a metal bump may be mounted on the semiconductor substrate.
The semiconductor substrate typically includes a silicon wafer substrate, but is not limited to this, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.

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

≪Support≫
The support is a member that supports the semiconductor substrate or the electronic device. As will be described later, the support may have a property of transmitting light and may include a support base that is a member that supports the semiconductor substrate, and a separation layer that is altered by irradiation of light.

<Component that forms a crosslinked structure by heat and the crosslinked structure is decomposed by an acid or an alkali: (C) component>
The adhesive composition according to the present embodiment forms a cross-linked structure by heat and is cured to form an adhesive layer between the semiconductor substrate or the electronic device and the support, and temporarily adheres the member. .. Furthermore, the crosslinked structure has a property of being decomposed by an acid or an alkali, and the adhesive layer can be easily removed by a treatment liquid containing an acid or an alkali. Therefore, the adhesive composition of the present embodiment is a component (hereinafter, also referred to as “(C) component”) that has a property of forming a crosslinked structure by heat and curing, and having the property that the crosslinked structure is decomposed by an acid or an alkali. Is included).
The component is not particularly limited, but examples thereof include a component that forms a urethane bond by heat. Examples of the component that forms a urethane bond by heat include a polyisocyanate compound and a polyol.

<<Polyisocyanate compound: (I) component>>
The adhesive composition of this embodiment may contain a polyisocyanate compound (hereinafter, also referred to as “component (I)”) as component (C). In the present specification, the "polyisocyanate compound" means a compound (polyisocyanate) having two or more isocyanate groups (-N=C=O) or a compound having two or more blocked isocyanate groups (block poly (Isocyanate). The polyisocyanate is not particularly limited, and those generally used in the production of urethane resin can be used without particular limitation.
Blocked polyisocyanate is a compound in which an isocyanate group of polyisocyanate is blocked by a reaction with a blocking agent to be inactivated. The blocked polyisocyanate used as the component (I) preferably has an isocyanate group blocked by a heat dissociative blocking agent. Examples of the heat dissociable blocking agent include blocking agents such as oximes, diketones, phenols and caprolactams. In the blocked polyisocyanate prepared by the heat dissociative blocking agent, the isocyanate group is inactive at room temperature, and when heated, the heat dissociable blocking agent dissociates to regenerate the isocyanate group.

Specific examples of polyisocyanates include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, Alicyclic diisocyanates such as hydrogenated tolylene diisocyanate and dicyclohexylmethane-4,4'-diisocyanate; and tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate , Aromatic diisocyanates such as tolidine diisocyanate, p-phenylene diisocyanate, and naphthylene diisocyanate; and biuret bodies, isocyanurate bodies, and trimethylolpropane adduct bodies thereof. The polyisocyanates may be used alone or in combination of two or more.

A commercially available polyisocyanate may be used. Examples of commercially available polyisocyanates include Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, 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. (These are the product names and the product name of Asahi Kasei Chemicals Corporation). These products may be used alone or in combination of two or more.

Examples of the blocked isocyanate include compounds in which the isocyanate group of the polyisocyanate as described above is protected by a reaction with a blocking agent. The blocking agent is not particularly limited as long as it is a thermal dissociative blocking agent, that is, a compound that is added to an isocyanate group and is stable at room temperature, but is liberated to form an isocyanate group when heated to a dissociation temperature or higher, Any thing can be used without particular limitation.
Specific examples of the blocking agent include, for example, lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; methylethylketoxime, methylisoamylketoxime, methylisobutylketoxime, formamideoxime, acetamideoxime, and the like. Oxime compounds such as acetoxime, diacetyl monooxime, benzophenone oxime and cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol and nitrophenol; polycyclic phenol compounds such as 1-naphthol; methyl alcohol, ethyl alcohol, isopropyl alcohol , Tert-butyl alcohol, trimethylolpropane, 2-ethylhexyl alcohol and other alcohol compounds; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and other ether compounds; malonic acid alkyl ester, malonic acid dialkyl ester, aceto Active methylene compounds such as acetic acid alkyl ester and acetylacetone; and the like. As the blocking agent, one type may be used alone, or two or more types may be used in combination.

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

As the blocked polyisocyanate, commercially available products may be used. Examples of 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, trade name. , Manufactured by Asahi Kasei Co., Ltd.) and the like.

As the component (I), a blocked polyisocyanate in which an isocyanate group is blocked by a heat dissociative blocking agent is preferable.
As the component (I), one type may be used alone, or two or more types may be used in combination.
The content of the component (I) in the adhesive composition of the present embodiment is, for example, 5 to 50 mass% with respect to the total amount of the component (C), and preferably 10 to 40 mass %.

<<Polyol: (P) component>>
The adhesive composition of the present embodiment may contain a polyol (hereinafter, also referred to as “(P) component”) as the (C) component. A polyol is a compound having two or more hydroxy groups (-OH). The polyol is not particularly limited, and those generally used in the production of urethane resin can be used without particular limitation.

Specific examples of the polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkanediol having 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 having 17 to 20 carbon atoms, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1, Dihydric alcohols such as 4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol and bisphenol A; Trihydric alcohols such as glycerin and trimethylolpropane; Tetramethylolmethane (pentaerythritol) , Diglycerin and other tetrahydric alcohols; xylitol and other pentahydric alcohols; sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol and other hexahydric alcohols; perseitol and other 7hydric alcohols; and sucrose. Octahydric alcohols such as; and the like.

Further, the polyol is a phenol resin, a resin containing a hydroxystyrene skeleton, a polyester polyol, a polyether polyol, a polyether ester polyol, a polyester amide polyol, an acrylic polyol, a polycarbonate polyol, a polyhydroxyl alkane, a polyurethane polyol, castor oil or a mixture thereof ( Hereinafter, these may be referred to as polyols (1)) and other polymer polyols. In this case, the number average molecular weight of the polyol is preferably 500 to 100,000 from the viewpoint of the viscosity of the adhesive composition.

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

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

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p. -Hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic aldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenyl Examples thereof include benzaldehyde.

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

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

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

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. 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 of 1 to 3. ]

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

In the formula (a10-1), Ya ^x1 represents a single bond or a divalent linking group.
Preferred examples of the divalent linking group for Ya ^x1 include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom.

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

.. Aliphatic hydrocarbon group in Ya ^x1 The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and carbon. Numbers 1 to 4 are more preferable, and numbers 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.
The branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{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 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; alkyltrimethylene group such as —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —; —CH(CH ₃ ). Examples thereof include alkyl alkylene groups such as alkyl tetramethylene groups such as CH ₂ CH ₂ CH ₂ — and —CH ₂ CH(CH ₃ )CH ₂ CH ₂ —. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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

...Aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, the cyclic fat Examples thereof include a group in which a group hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include the same ones as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a 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.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group, Most preferred are methoxy and ethoxy groups.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.
In the cyclic aliphatic hydrocarbon group, a part of 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.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably has 5 to 20 carbon atoms, still more preferably has 6 to 15 carbon atoms, and particularly preferably has 6 to 12 carbon atoms. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group in which two hydrogen atoms have been removed from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms in a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle A group in which one is substituted with an alkylene group (for example, a hydrogen atom from an aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). Groups in which one more atom has been removed) and the like. The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a 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, a hydroxyl group and the like.
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 the substituent for substituting the hydrogen atom contained in the cyclic aliphatic hydrocarbon group.

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

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

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

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

Below, the specific example of the structural unit represented by the said general formula (a10-1) is 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 more preferably a polymer of hydroxystyrene (polyhydroxystyrene).

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

As the polyether polyol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran is polymerized by using, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, or a low-content polyol such as glycerin as an initiator. The resulting polyether polyol may be mentioned.

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

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

Examples of the acrylic polyol include hydroxyethyl acrylate having one or more hydroxyl groups in one molecule, hydroxypropyl acrylate, acrylhydroxybutyl, etc., or their corresponding methacrylic acid derivatives, such as acrylic acid, methacrylic acid or The polyester amide polyol obtained by copolymerizing with the ester is mentioned.

Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol and 1,9-nonane. One or more of diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, etc. Polycarbonate polyols obtained by reacting the above glycol with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, and the like.

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

The polyurethane polyol is a polyol having one or more urethane bonds in one molecule, and includes, for example, a polyether polyol having a number average molecular weight of 200 to 20,000, a polyester polyol, a polyether ester polyol and the like, and a polyisocyanate. A polyurethane polyol obtained by reacting with NCO/OH of less than 1, more preferably 0.9 or less is preferable.

Among the above, as the component (P), a phenol resin or a resin containing a hydroxystyrene skeleton is preferable, a novolac resin or a resin containing a hydroxystyrene skeleton is more preferable, and a polymer of hydroxystyrene or a hydroxystyrene derivative is further preferable, Polyhydroxystyrene resins are particularly preferred.

As the component (P), one type may be used alone, or two or more types may be used in combination.
The content of the component (P) in the adhesive composition of the present embodiment is, for example, 50 to 95 mass% with respect to the total amount of the component (C), and preferably 60 to 90 mass %.

The adhesive composition of the present embodiment preferably contains the above component (I) and component (P) as the component (C). In this case, the molar ratio (NCO/OH) of the hydroxy group (-OH) in the component (P) to the isocyanate group (-NCO) in the component (I) contained in the adhesive composition of the present embodiment is It is preferably 0.1 to 1, and more preferably 0.3 to 0.7.
Further, the ratio of the contents of the component (I) and the component (P) contained in the adhesive composition of the present embodiment ((I) component mass:(P) component mass) is 1:10 to 10:1. Is more preferable, and the range is more preferably 2:8 to 8:2, further preferably 2:8 to 5:5.

<Other ingredients>
The adhesive composition of the present embodiment may contain other components in addition to the component (C) as long as the effects of the present invention are not impaired. Other components are not particularly limited, and for example, various commonly used additives such as release agents, plasticizers, adhesion aids, stabilizers, colorants, surfactants, curing reaction accelerators, etc. may be used. it can. Further, the adhesive may contain a diluent solvent. The diluent solvent may be one that is inert to the component (C), and examples thereof include ester solvents such as ethyl acetate, ketone solvents such as methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene and xylene. ..

According to the adhesive composition of the present embodiment, when temporarily adhering the semiconductor substrate or the electronic device and the support, the adhesive layer is formed by forming a cross-linking structure by heat and curing the semiconductor, The substrate or electronic device and the support are bonded together. Since the adhesive layer is formed by an adhesive layer that is cured by forming a cross-linking structure by heat, it has high heat resistance, and even when high temperature treatment is performed during processing of a semiconductor substrate or an electronic device, misalignment or sinking occurs. It is difficult for problems such as
On the other hand, the crosslinked structure in the adhesive layer can be decomposed by an acid or an alkali. Therefore, the processing of the semiconductor substrate or the electronic device on the support is completed, and when the semiconductor substrate or the electronic device and the support are separated, an acid or an alkali acts on the adhesive layer to form a crosslinked structure. Is decomposed and the adhesive layer is removed. Thereby, the semiconductor substrate or the electronic device and the support can be easily separated. Further, the residue of the adhesive layer attached to the semiconductor substrate or the electronic device can be easily removed by using acid or alkali.

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

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

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

FIG. 3 shows still another embodiment of the laminated body according to the second aspect.
The laminated body 300 illustrated in FIG. 3 has the same configuration as the laminated body 100 except that the electronic device includes the wiring layer 6.

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

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

<<Supporting substrate>>
The supporting substrate has a property of transmitting light and is a member that supports a semiconductor substrate or an electronic component. When the separation layer is provided as in FIGS. 1 to 4, the supporting substrate is attached to the semiconductor substrate or the electronic device via the separation layer and the adhesive layer. When the separation layer is not provided, the supporting substrate is attached to the semiconductor substrate or the electronic device via the adhesive layer. Therefore, it is preferable that the supporting substrate has a strength necessary to prevent damage or deformation of the semiconductor substrate during thinning of the device, transportation of the semiconductor substrate, mounting on the semiconductor substrate, or the like. When the support has a separation layer, the support substrate is preferably one that transmits light having a wavelength that can change the quality of the separation layer.
As the material of the supporting base, for example, glass, silicon, acrylic resin or the like is used. Examples of the shape of the support base include, but are not limited to, a rectangle and a circle.
Further, as the supporting substrate, a circular supporting substrate having a large size or a large panel having a quadrangular shape in a plan view can be used for further high-density integration and improving production efficiency.

≪Separation layer≫
The separation layer is a layer that is adjacent to the adhesive layer, is altered by irradiation of light, and can separate the supporting base from the semiconductor substrate or the electronic device fixed to the supporting body via the adhesive layer.
This separation layer can be formed using the composition for forming a separation layer described below, and for example, by firing the components contained in the composition for forming the separation layer, or by a chemical vapor deposition (CVD) method. It is formed. This separation layer is preferably altered by absorbing the light that is transmitted and radiated through the supporting substrate.
The separation layer is preferably formed of only a material that absorbs light, but is a layer in which a material that does not have a structure that absorbs light is compounded within a range that does not impair the essential characteristics of the present invention. It may be.

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

The separation layer preferably has a flat surface on the side in contact with the adhesive layer (no unevenness is formed), which facilitates formation of the adhesive layer, and allows the semiconductor substrate or the electronic device and the supporting substrate to be formed. It becomes easy to attach and evenly.

Separation Layer-Forming Composition The separation layer-forming composition, which is a material for forming the separation layer, is, for example, fluorocarbon, a polymer having a repeating unit containing a light-absorbing structure, an inorganic material, an infrared ray. Examples thereof include a compound having an absorptive structure, an infrared absorbing substance, a reactive polysilsesquioxane, or a resin component having a phenol skeleton.
In addition, the composition for forming the separation layer improves the separability of the filler, the plasticizer, the thermal acid generator component, the photoacid generator component, the organic solvent component, the surfactant, the sensitizer, or the supporting substrate as an optional component. Ingredients that may be added may be contained.

..Fluorocarbon separation layer may contain fluorocarbon. The separation layer made of fluorocarbon is modified by absorbing light, and as a result, loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support can be easily separated from the semiconductor substrate or the electronic device. The fluorocarbon forming the separation layer can be preferably formed by a plasma CVD method.
Fluorocarbons absorb light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength in the range absorbed by the fluorocarbon used for the separation layer, the fluorocarbon can be suitably altered. The absorption rate of light in the separation layer is preferably 80% or more.

The light for irradiating the separation layer may be, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, a solid-state laser such as an LD laser or a fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that can be absorbed by the fluorocarbon. , 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 used as appropriate. As the wavelength that can change the quality of the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

..Polymer Having Repeating Units Having Structure Having Light Absorption The separation layer may contain a polymer having repeating units having a structure having light absorption. The polymer is altered by being irradiated with light.
Examples of the light-absorbing structure include an atomic group containing a conjugated π electron system including a substituted or unsubstituted benzene ring, a condensed ring, or a heterocycle. More specifically, the structure having a light absorbing property is a cardo structure, or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), or a diphenyl structure present in a side chain of the polymer. A structure or a diphenylamine structure is mentioned.
The above-mentioned light-absorbing structure 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 above light absorption property is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

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

..Inorganic substance The separation layer may be made of an inorganic substance. The inorganic substance may be any substance that is altered by absorbing light, and for example, one or more kinds selected from the group consisting of metals, metal compounds and carbon are suitable. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.
Examples of such an inorganic material include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon.
Note that carbon is a concept that may include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like.
The inorganic substance absorbs light having a wavelength in a specific range depending on its type.

The light for irradiating the separation layer made of an inorganic substance may be, for example, a solid-state laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, or a dye laser, depending on the wavelength that can be absorbed by the inorganic substance. Liquid laser such as CO ₂ laser, excimer laser, Ar laser, gas laser such as He—Ne laser, semiconductor laser, laser light such as free electron laser, or non-laser light may be used as appropriate.
The separation layer made of an inorganic material can be formed on the supporting substrate by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating.

..Compound having infrared absorbing structure The separation layer may contain a compound having an infrared absorbing structure. This compound having an infrared absorbing structure is altered by absorbing infrared rays.
Examples of the structure having infrared absorption property or the compound having this structure include alkane, alkene (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, cyclic), alkyne ( Substituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohols or phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated secondary, saturated tertiary , Unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 -Enol of diketone, o-hydroxyaryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylate anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β -, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride (conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, Primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary Secondary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, Aromatic nitro compounds, nitroamines, nitrosamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatics, monomers, dimers), sulfur compounds such as mercaptans or thiophenols or thiol acids, thiocarbonyl groups, Sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), P-A ^2. A bond (A ² is H, C or O) or a Ti—O bond is included.

As a structure containing halogen bond, for example _{-CH 2 Cl, -CH 2 Br,} -CH 2 I, -CF 2 - - Additional _{carbon, - CF 3, -CH = CF} 2, -CF = CF 2, fluoride And aryl chloride.

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

The structure includes a ^{P-A 2} bonds described above, for _{example, PH, PH 2, P-} CH 3, P-CH 2 -, P-C 6 H 5, A 3 3 -P-O (A 3 fat Group or aromatic group), (A ⁴ O) ₃ -P-O (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , P-O-P. , P-OH or O=P-OH and the like.

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium or titanium-i-propoxyoctyleneglycolate. Alkoxy titanium; (ii) di-i-propoxy bis(acetylacetonato) titanium or chelate titanium such as propanedioxytitanium bis(ethylacetoacetate); (iii) i-C ₃ H ₇ O-[-Ti( _{O-i-C 3 H 7} ) 2 -O-] n -i-C 3 H 7 or _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O-] n titanium polymers such _{-n-C 4 H 9; (} iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisostearate or (2-n-butoxycarbonyl benzoyloxy) Examples thereof include acylate titanium such as tributoxytitanium; and (v) water-soluble titanium compounds such as di-n-butoxybis(triethanolaminato)titanium.
Among these, as a compound containing a Ti—O bond, di-n-butoxy bis(triethanolaminato)titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH)) ₂ ] ₂ ) is preferred.

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

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 document: SILVERSTEIN, BASLER, MORRILL, “Spectral identification method of organic compounds (fifth edition)-combination of MS, IR, NMR, and UV-” (published in 1992) The description on pages 146 to 151 can be referred to.

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

..Infrared absorbing substance The separation layer may contain an infrared absorbing substance. The infrared absorbing substance may be any substance as long as it is modified by absorbing light, and for example, carbon black, iron particles, or aluminum particles can be preferably used.
The infrared absorbing material absorbs light having a wavelength in a specific range depending on its type. By irradiating the separation layer with light having a wavelength in the range that the infrared absorption material used for the separation layer absorbs, the infrared absorption material can be suitably altered.

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

"Reactive polysilsesquioxane" refers to a polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. .. The silanol groups or functional groups capable of forming silanol groups can be condensed together to polymerize with each other. Further, the reactive polysilsesquioxane, silanol group, or, if it has a functional group capable of forming a silanol group, a random structure, a cage structure, a silsesquioxane skeleton such as a ladder structure. The reactive polysilsesquioxane provided can be employed.

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

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

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

.. 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 denatured (oxidized, etc.) by heating or the like and photoreactivity is enhanced.
The term “having a phenol skeleton” as used herein means containing a hydroxybenzene structure.
The resin component having a phenol skeleton has a film forming ability and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1,000 to 30,000, further preferably 1,500 to 20,000, particularly preferably 2,000 to 15,000. When the molecular weight of the resin component is not more than the upper limit value of the above-mentioned preferable range, the solubility of the composition for forming a separation layer in a solvent is enhanced.
As the molecular weight of the resin component, a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography) is used.

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

<Adhesive layer>
The adhesive layer is provided for temporarily adhering the semiconductor substrate or the electronic device to the support. The adhesive layer is a cured product of the adhesive composition according to the first embodiment. More specifically, the adhesive layer is formed by thermosetting the adhesive composition according to the first embodiment. The thickness of the adhesive layer is, for example, preferably in the range of 1 μm or more and 200 μm or less, more preferably in the range of 5 μm or more and 150 μm or less.

Further, the adhesive layer of the present embodiment is a cured body of the adhesive composition as described above, but the material (cured body) forming the adhesive layer preferably satisfies the following characteristics.
That is, when the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 50° C. is preferably 1.0×10 ⁸ Pa or more, and 5.0×10 ⁸ Pa or more. It is more preferable that it is 1.0×10 ⁹ Pa or more. The upper limit of the complex elastic modulus at 50° C. is, for example, 1.0×10 ¹⁰ Pa or less.
Further, when the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 200° C. is preferably 1.0×10 ⁴ Pa or more, and 5.0×10 ⁴ Pa or more. Is more preferable, and 1.0×10 ⁵ Pa or more is further preferable. The upper limit of the complex elastic modulus at 200° C. is, for example, 1.0×10 ⁸ or less.

The complex elastic modulus of the cured product can be measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). Specifically, the adhesive composition was coated on a PET film with a release agent and heated in an oven under atmospheric pressure at 90° C. for 5 minutes and then at 200° C. for 60 minutes to test a thickness of 20 μm. A test piece (size 0.5 cm×1 cm, thickness 20 μm) formed by forming a piece and then peeled off from the PET film can be measured using the above-described measuring device.
Further, as the measurement conditions, under the tensile condition of frequency 1 Hz, the condition of increasing the temperature from the starting temperature of 40° C. to 240° C. at the temperature rising rate of 5° C./min may be adopted.

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

<<Semiconductor Substrate>>
The semiconductor substrate is not particularly limited, and examples thereof are the same as those exemplified in the above “(Adhesive composition)”. The semiconductor substrate may be a semiconductor device or other device, and may have a single-layer or multi-layer structure.

≪Electronic device≫
The electronic device is not particularly limited, and examples thereof are the same as those exemplified in the above “(Adhesive composition)”. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. Specifically, the electronic device may include at least one of a sealing material layer and a wiring layer, and may further include a semiconductor substrate.
In the laminated body 200 shown in FIG. 2, the electronic device 456 includes the semiconductor substrate 4, the encapsulating material layer 5, and the wiring layer 6. In the laminated body 300 shown in FIG. 3, the electronic device 6 is composed of the wiring layer 6. In the laminated body 400 shown in FIG. 4, the electronic device 645 includes the wiring layer 6, the semiconductor substrate 4, and the encapsulating material layer 5.

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

<< Wiring layer >>
The wiring layer is also called an RDL (Redistribution Layer), is a thin-film wiring body that constitutes a wiring connected to the substrate, and may have a single-layer or multi-layer structure. The wiring layer includes a conductor (for example, a metal such as aluminum, copper, titanium, nickel, gold and silver, and silver-tin) between a dielectric (a silicon oxide (SiO _x ), a photosensitive resin such as a photosensitive epoxy). However, the present invention is not limited to this.

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

(Method for manufacturing laminated body (1))
A method for manufacturing a laminated body according to a third aspect of the present invention is a method for manufacturing a laminated body in which a support, an adhesive layer, and a semiconductor substrate are laminated in this order, and the support or the semiconductor substrate is provided with the first Adhesive composition layer forming step of applying an adhesive composition according to an aspect to form an adhesive composition layer, and placing the semiconductor substrate on the support through the adhesive composition layer And a semiconductor substrate mounting step, and heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer and cure the adhesive composition layer to form an adhesive layer. It is characterized by

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

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

The method for forming the adhesive composition layer 3′ on the support 12 is not particularly limited, and examples thereof include spin coating, dipping, roller blade, spray coating, and slit coating.
The adhesive composition layer may be formed on the semiconductor substrate 4 by the same method.

Baking may be performed after forming the adhesive composition layer. The baking temperature condition is a temperature lower than the heating temperature in the adhesive layer forming step described later. The baking conditions may vary depending on the type of the component (C) contained in the adhesive composition, and examples thereof include temperature conditions of 70 to 100° C. and 1 to 10 minutes.

[Semiconductor substrate mounting process]
The method for manufacturing a laminated body according to this embodiment includes a semiconductor substrate mounting step. The semiconductor substrate mounting step is a step of mounting the semiconductor substrate on the support via the adhesive composition layer. Thereby, the laminated body 100′ can be obtained.
In FIG. 5C, the semiconductor substrate 4 is placed on the support 12 via the adhesive composition layer 3 ′ formed on the support 12.

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

[Adhesive layer forming process]
The method for manufacturing a laminate according to this embodiment includes an adhesive layer forming step. The adhesive layer forming step is a step of forming an adhesive layer by heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer and curing it. Thereby, the laminated body 100 can be obtained.
In FIG. 6, the adhesive layer 3 is formed by heating the adhesive composition layer 3′.

The heating temperature in this step may be appropriately selected according to the thermosetting temperature of the component (C) contained in the adhesive composition used for forming the adhesive composition layer 3′. For example, when the component (C) contains the component (I) and the component (P), the heating temperature can be equal to or higher than the temperature at which the crosslinking reaction of the component (I) and the component (P) is started. For example, when the component (I) contains a blocked polyisocyanate, the heating temperature in this step can be a temperature equal to or higher than the dissociation temperature of the heat dissociative blocking agent that blocks the isocyanate group in the blocked polyisocyanate. The heating temperature may vary depending on the type of the heat dissociative blocking agent, and examples thereof include 80°C or higher, 100°C or higher, 130°C or higher, or 150°C or higher. The upper limit of the heating temperature is not particularly limited, but from the viewpoint of energy consumption, for example, 350° C. or lower, 300° C. or lower, 250° C. or lower, etc. may be mentioned. Examples of the heating temperature range include 80 to 350°C, 100 to 300°C, 130 to 300°C, and 150 to 300°C.
The heating time is not particularly limited as long as it is a time sufficient for thermosetting the component (C), and can be, for example, 15 minutes or more, 30 minutes or more, or 45 minutes or more. The upper limit of the heating time is not particularly limited, but may be, for example, 120 minutes or less, 100 minutes or less, 80 minutes or less, or 60 minutes or less from the viewpoint of work efficiency and the like. Examples of the heating time range include 15 to 120 minutes, 30 to 120 minutes, and 45 to 120 minutes.

By this step, the component (C) in the adhesive composition layer 3'forms a crosslinked structure and is 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 laminated body 100 can be obtained.

[Arbitrary process]
The method for manufacturing a laminated body according to this embodiment may include other steps in addition to the above steps. Other steps include, for example, a separation layer forming step, and various mechanical or chemical treatments (such as thinning treatments such as gliding and chemical mechanical polishing (CMP), chemical vapor deposition (CVD) and physical vapor deposition (CVD)). (Eg, PVD) under high temperature/vacuum, treatment with chemicals such as organic solvent, acidic treatment liquid or basic treatment liquid, plating treatment, irradiation with actinic rays, heating/cooling treatment, etc.).

-Separation layer formation process When a support contains a separation layer, the manufacturing method of the layered product concerning this embodiment may include a separation layer formation process. The separation layer forming step is a step of forming a separation layer on one side of the supporting substrate using the composition for forming a separation layer.
In FIG. 5A, the separating layer 2 is formed on the supporting substrate 1 by using the separating layer forming composition (containing a fluorocarbon) (that is, a supporting substrate with a separating layer is produced. Exist).

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

(Method for manufacturing laminated body (2))
A method for manufacturing a laminated body according to a fourth aspect of the present invention is a method for manufacturing a laminated body according to the third aspect, wherein a laminated body is obtained, and then a member composed of a metal or a semiconductor and the member are sealed. It is characterized by further comprising an electronic device forming step of forming an electronic device which is a composite of a resin for stopping or insulating.

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

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

-About a sealing process A sealing process is a process which seals the board|substrate fixed on the support body using a sealing material.
In FIG. 7A, a laminated body 110 is obtained in which the entire semiconductor substrate 4 temporarily adhered to the support 12 via the adhesive layer 3 is sealed with the sealing material layer 5.

In the sealing step, a sealing material heated to, for example, 130 to 170° C. is supplied onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high viscosity state, and compression molded. Thus, the laminated body 110 in which the sealing material layer 5 is provided on the adhesive layer 3 is manufactured.
At that time, the temperature condition is, for example, 130 to 170°C.
The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500 N/cm ² .

The encapsulating material layer 5 is not provided for each individual semiconductor substrate 4, but is preferably provided so as to cover the entire semiconductor substrate 4 on the adhesive layer 3.

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

-Wiring layer forming step The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor substrate after the grinding step.
In FIG. 7C, the wiring layer 6 is formed on the semiconductor substrate 4 and the sealing material layer 5. Thereby, the laminated body 120 can be obtained. In the laminated body 120, the semiconductor substrate 4, the encapsulating material layer 5, and the wiring layer 6 form an electronic device 456.

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

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

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

(Method for manufacturing laminated body (3))
A method for producing a laminated body according to a fifth aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer and an electronic device are laminated in this order, and the method according to the first aspect is provided on the support. An adhesive composition layer forming step of applying the adhesive composition to form a layer of the adhesive composition; a member made of a metal or a semiconductor; and a resin for sealing or insulating the member. An electronic device that is a composite, an electronic device forming step of forming on the adhesive composition layer, and by heating the adhesive composition layer, to form a crosslinked structure in the adhesive composition layer And an adhesive layer forming step of forming an adhesive layer by curing.

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

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

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

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

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

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

(Method of manufacturing electronic components)
A method for manufacturing an electronic component according to a sixth aspect of the present invention is a method for manufacturing a laminated body according to any one of the third to fifth aspects, after obtaining a laminated body, the crosslinked structure in the adhesive layer. And an adhesive layer removing step of removing the adhesive layer by decomposing the adhesive layer with an acid or an alkali.
When the support is composed of a support base and a separation layer, the method according to the present embodiment is characterized in that the separation layer is irradiated with light through the support base before the adhesive layer removing step. The method may further include a separation step of separating the electronic device and the supporting substrate by degrading.

FIG. 8 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). FIG. 8A is a diagram showing the laminated body 120, FIG. 8B is a diagram illustrating the separating step, and FIG. 8C is a diagram illustrating the adhesive removing step.

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

The wavelength that can change the quality of the separation layer 2 includes, for example, a range of 600 nm or less.
The type and wavelength of the light to be irradiated may be appropriately selected according to the transparency of the support base 1 and the material of the separation layer 2, and examples thereof include YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber. A solid laser such as a laser, a liquid laser such as a dye laser, a CO ₂ laser, an excimer laser, an Ar laser, a gas laser such as a He-Ne laser, a semiconductor laser, a laser light such as a free electron laser, or a non-laser light can be used. it can. As a result, the separation layer 2 can be altered so that the support base 1 and the electronic device 456 can be easily separated.

When irradiating with a laser beam, the following conditions can be mentioned as an example of a laser beam irradiating condition.
The average output value of the laser light is preferably 1.0 W or more and 5.0 W or less, 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 the separation layer 2 with light (arrow) to change the quality of the separation layer 2, the supporting substrate 1 is separated from the electronic device 456 as shown in FIG. 8B.
For example, the support base 1 and the electronic device 456 are separated from each other by applying a force in a direction in which the support base 1 and the electronic device 456 are separated from each other. Specifically, one of the support base 1 and the electronic device 456 side (wiring layer 6) is fixed to the stage, and the other is lifted while being suction-held by a separation plate equipped with a suction pad such as a bellows pad. The support base 1 and the electronic device 456 can be separated.
The force applied to the laminate 200 may be appropriately adjusted according to the size of the laminate 200 and the like, and is not limited. For example, in the case of a laminate having a diameter of about 300 mm, 0.1 to 5 kgf (0 The supporting substrate 1 and the electronic device 456 can be suitably separated by applying a force of about 0.98 to 49 N).

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

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

In this step, the acid or alkali used for decomposing the crosslinked structure in the adhesive layer 3 is not particularly limited as long as it can decompose the crosslinked structure. For example, when the crosslinked structure is composed of urethane bonds, an acid or alkali that can decompose the urethane bonds may be used. Examples of the acid capable of decomposing the urethane bond include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of alkalis capable of decomposing urethane bonds include, but are not limited to, inorganic bases such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine.

The 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 thereof include dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, and propylene glycol.
The treatment liquid for removing the adhesive may contain known additives such as a surfactant in addition to the above components.
The content of the acid or alkali in the treatment liquid is not particularly limited, and examples thereof include 1 to 50 mass %. Moreover, as content of the polar solvent in the said process liquid, 50-99 mass% is mentioned.
By bringing the treatment liquid containing an acid or an alkali into contact with the adhesive layer 3, the crosslinked structure in the adhesive layer 3 is decomposed and the adhesive layer 3 can be removed.

According to the method for manufacturing an electronic component according to the present embodiment, a semiconductor substrate or an electronic substrate is formed by using an adhesive composition in which a crosslinked structure is formed by heat and cured, and the crosslinked structure is decomposed by an acid or an alkali. Since the device and the support are temporarily adhered to each other, it is possible to form an adhesive layer having high heat resistance that can withstand high-temperature treatment in an electronic device forming process or the like. Further, since the crosslinked structure in the adhesive layer is decomposed by acid or alkali, the adhesive layer can be easily washed and removed after completion of the electronic device forming process and the like.

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

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

<Preparation of adhesive composition>
(Examples 1 and 2)
The components shown in Table 1 were mixed to prepare the adhesive composition of each example.

In Table 1, each abbreviation has the following meanings. The numerical value in [] is a compounding amount (part by mass).

(P)-1: Novolac-type phenol resin (MEHC-7841-3H (trade name), manufactured by Meiwa Kasei Co., Ltd.).
(P)-2: Polyhydroxystyrene resin (VPS-2515 (trade name), manufactured by Nippon Soda Co., Ltd.).
(I)-1: Adduct type block polyisocyanate (E402-B80B (trade name), manufactured by Asahi Kasei Corporation).
(Ad)-1: Surfactant (BYK0310 (trade name), manufactured by BYK).

<Evaluation>
≪Heat resistance≫
The heat resistance was evaluated by measuring the complex elastic modulus of the cured product of the adhesive composition.
The adhesive composition of each example was applied onto a PET film with a release agent, and heated in an oven under atmospheric pressure at 90° C. for 5 minutes and then at 200° C. for 60 minutes to form a test piece ( Thickness 20 μm). Then, the complex elastic modulus of the test piece (size 0.5 cm×1 cm, thickness 20 μm) peeled from the PET film was measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.).
The measurement conditions were such that the starting temperature was 40° C. to 240° C. and the temperature was raised at a heating rate of 5° C./min under the tension condition of frequency 1 Hz.

FIG. 9 is a graph showing the behavior of the complex elastic modulus with respect to temperature for the test piece (adhesive layer) formed using the adhesive composition of each example. As shown in FIG. 9, the adhesive compositions of Examples 1 and 2 maintained a high complex elastic modulus in a substantially constant range in a high temperature part (about 150° C. or higher).

<<Removability>>
The adhesive composition of each example was applied onto a glass supporting substrate (size diameter 30 cm, thickness 1000 μm) by a spin coating method while rotating at 1000 rpm. Next, the supporting substrate coated with the adhesive composition of each example was heated at 90° C. for 5 minutes and at 200° C. for 60 minutes to form an adhesive layer having a thickness of 50 μm.

The adhesive layer of each example was treated at room temperature (23° C.) with a treatment solution (tetramethylammonium hydroxide (TMAH) mixed solvent of N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO) (NMP:DMS=50: 50 (mass ratio)) diluted with a concentration of 2% by mass), and the time required for complete dissolution was measured. The dissolution rate of the adhesive layer in each example was calculated from the dissolution time with respect to the film thickness. The results are shown in Table 2.

From the results shown in Table 2, it was confirmed that the adhesive layers formed using the adhesive compositions of Examples 1 and 2 were quickly dissolved in the treatment liquid and could be easily removed using the treatment liquid.

1 Support Substrate 2 Separation Layer 3 Adhesive Layer 3'Adhesive Composition Layer 4 Semiconductor Substrate 5 Encapsulant Layer 6 Wiring Layer 10 Intermediate Layer 12 Support 20 Laminate 50 Electronic Component 100 Laminate 100' Laminate 110 Laminate 120 Laminated body 200 Laminated body 300 Laminated body 400 Laminated body 456 Electronic device 645 Electronic device

Claims (11)

A semiconductor substrate or an electronic device, an adhesive composition used for forming an adhesive layer for temporarily adhering a support,
The adhesive composition is for performing the temporary adhesion by forming a crosslinked structure by heat and curing.
An adhesive composition, wherein the crosslinked structure is decomposed by an acid or an alkali, and the adhesive layer is removed during or after the decomposition process. The adhesive composition according to claim 1, wherein the crosslinked structure is formed by a urethane bond. The adhesive composition according to claim 1, comprising a polyisocyanate compound and a polyol. As the electronic device, a composite of a member formed of a metal or a semiconductor and a resin that seals or insulates the member is laminated on the support through the adhesive layer. Item 4. The adhesive composition according to item 3. A support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order,
The said adhesive layer is a laminated body which is a hardening body of the adhesive composition as described in any one of Claims 1-4. A method of manufacturing a laminated body in which a support, an adhesive layer and a semiconductor substrate are laminated in this order,
An adhesive composition layer forming step of forming an adhesive composition layer by applying the adhesive composition according to any one of claims 1 to 4 to the support or the semiconductor substrate,
A semiconductor substrate mounting step of mounting the semiconductor substrate on the support through the adhesive composition layer;
By heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer and cure it, an adhesive layer forming step of forming an adhesive layer,
A method for producing a laminate, comprising: After obtaining a laminate by the method for producing a laminate according to claim 6, an electronic device is formed which is a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member. Further comprising an electronic device forming step of
A method for producing a laminate, in which a support, an adhesive layer, and an electronic device are laminated in this order. A method for producing a laminate in which a support, an adhesive layer and an electronic device are laminated in this order,
An adhesive composition layer forming step of applying the adhesive composition according to any one of claims 1 to 4 on the support to form a layer of the adhesive composition,
An electronic device forming step of forming an electronic device, which is a composite of a member composed of a metal or a semiconductor, and a resin for sealing or insulating the member, on the adhesive composition layer,
By heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer and cure it, an adhesive layer forming step of forming an adhesive layer,
A method for producing a laminate, comprising: The support is composed of a support base and a separation layer that is altered by irradiation of light,
The method for producing a laminate according to claim 6, wherein the adhesive composition layer forming step is a step of forming an adhesive composition layer on the separation layer. After obtaining a laminate by the method for producing a laminate according to any one of claims 6 to 8,
Decomposing the crosslinked structure in the adhesive layer with an acid or an alkali, and having an adhesive layer removing step of removing the adhesive layer,
Electronic component manufacturing method. After obtaining a laminate by the method for producing a laminate according to claim 9,
A separation step of separating the electronic device and the supporting base by irradiating the separating layer with light through the supporting base to change the quality of the separating layer;
After the separation step, an adhesive layer removing step of decomposing the crosslinked structure in the adhesive layer with an acid or an alkali to remove the adhesive layer attached to the electronic device,
And a method for manufacturing an electronic component.

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