KR20200080129A - Adhesive composition, laminate, method of manufacturing laminate, and method of manufacturing electronic component - Google Patents

Abstract

Provided are an adhesive composition which has high heat resistance and produces an adhesive layer that is easily removable, a laminate manufactured by using the adhesive composition; a method of manufacturing the laminate; and a method of manufacturing an electronic component using the adhesive composition. In particular, the adhesive composition is used to form an adhesive layer that preliminary attaches a support to a semiconductor substrate or an electronic device, wherein the preliminary attachment is carried out as the adhesive composition forms a crosslinked structure by heat and thus is cured. Moreover, the crosslinked structure undergoes disintegration by an acid or an alkali, wherein the adhesive layer is removed during or after the process of the disintegration.

Description

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

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

Various types of semiconductor packages (electronic components) including semiconductor elements exist according to corresponding sizes, for example, WLP (Wafer Level Package), PLP (Panel Level Package), and the like.

As a technology of a semiconductor package, a fan doll technology and a fan out type technology are mentioned. As a semiconductor package by the fan doll technology, a fan doll WLP (Fan-in Wafer Level Package), etc., in which terminals at the end of a bare chip are rearranged in a chip area, is known. As a semiconductor package by the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package), which relocates its terminal outside the chip area, is known.

In recent years, in particular, the fan-out type technology has been applied to a fan-out panel level package (PLP) in which semiconductor devices are arranged and packaged on a panel, so that better integration, thinning, and miniaturization in semiconductor packages are achieved. It is attracting attention as a way to realize the back.

In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the device to be mounted. However, when the thickness of the substrate is made thin, the strength is lowered, and the substrate is easily damaged during semiconductor package manufacturing. On the other hand, a technique is known in which a substrate is temporarily adhered to a support using an adhesive, the substrate is processed, and the substrate is separated from the support.

As an adhesive used for temporary bonding of the substrate and the support, a thermoplastic adhesive is often used because it is easy to remove the adhesive layer 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

However, in semiconductor package manufacturing, high-temperature treatment such as thin film formation, firing, and die bonding may be performed. When the heat resistance of the adhesive is low, there is a concern that, during high temperature treatment, the substrate may be misaligned or the substrate may sink. On the other hand, when 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 for the adhesion between the support and the substrate, problems such as misalignment and sinking do not occur during high-temperature treatment, but it is difficult to remove the adhesive layer with a solvent or the like, and even when the separation layer is formed, After separating the support from the substrate by deterioration, it is difficult to remove the adhesive layer attached to the substrate.

This invention was made|formed in view of the said situation, the adhesive composition with high heat resistance and easy removal of an adhesive layer, the laminated body manufactured using the said adhesive composition, the manufacturing method of this laminated body, and the former using this adhesive composition It is an object to provide a method for manufacturing a part.

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

That is, the first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support, wherein the adhesive composition is cured by forming a crosslinked structure by heat to cure it. It is carried out, and the crosslinked structure is decomposed by acid or alkali, and the adhesive layer is removed during or after the decomposition process, and the adhesive layer is removed.

The 2nd aspect of this invention is a laminated body in which the support body, an adhesive layer, and a semiconductor substrate or an electronic device were laminated|stacked in this order, The said adhesive layer is a laminated body which is hardened|cured material of the adhesive composition which concerns on the said 1st aspect.

A third aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer and a semiconductor substrate are stacked in this order, and the adhesive composition according to the first aspect is applied to the support or semiconductor substrate to form an adhesive composition layer. Crosslinking in the adhesive composition layer by heating the adhesive composition layer, and a semiconductor substrate mounting process for placing the semiconductor substrate on the support through the adhesive composition layer, and heating the adhesive composition layer. It is a manufacturing method of a laminated body which has the adhesive layer formation process which forms a structure and hardens and forms an adhesive layer.

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

A fifth aspect of the present invention is a method for producing a laminate in which a support body, an adhesive layer and an electronic device are stacked in this order. On the support body, the adhesive composition according to the first aspect is applied to form a layer of the adhesive composition. The adhesive composition layer forming process to be performed, and the electronic device forming process of forming an electronic device which is a composite of a member formed of a metal or a semiconductor and a resin sealing or insulating the member on the adhesive composition layer, and the adhesive composition It is a manufacturing method of a laminated body which has the adhesive layer formation process which forms a bonding layer by hardening by forming a crosslinked structure in the said adhesive composition layer by heating a layer.

In the sixth aspect of the present invention, after obtaining the laminate by the method for producing a laminate according to any of the third to fifth aspects, the crosslinked structure in the adhesive layer is decomposed with acid or alkali to dissolve the adhesive layer. It is a manufacturing method of an electronic component which has the process of removing the adhesive layer to remove.

In the seventh aspect of the present invention, after obtaining the laminate by the method for producing a laminate according to any of the third to fifth aspects, the separation layer is irradiated with light through the support gas to irradiate the separation layer. By altering, the separation step for separating the electronic device from the support gas, and the adhesive layer for decomposing the crosslinked structure in the adhesive layer with acid or alkali after the separation step to remove the adhesive layer attached to the electronic device It is a manufacturing method of an electronic component which has a removal process.

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

1 is a schematic view showing an embodiment of a laminate to which the present invention is applied.
2 is a schematic view showing an embodiment of a laminate to which the present invention is applied.
3 is a schematic view showing an embodiment of a laminate to which the present invention is applied.
4 is a schematic view showing an embodiment of a laminate to which the present invention is applied.
5 is a schematic process diagram for explaining an embodiment of a method for manufacturing a laminate 100 ′ in which a support, an adhesive composition layer, and a semiconductor substrate are laminated in this order. Fig. 5(a) is a view showing a support made of a support gas and a separation layer, Fig. 5(b) is a view for explaining a process for forming an adhesive composition layer, and Fig. 5(c) is a semiconductor substrate mounting process. It is an explanatory drawing.
It is a figure explaining an adhesive layer formation process.
7 is a schematic process diagram for explaining an embodiment of a method for manufacturing the laminate 120. Fig. 7(a) is a diagram for explaining the sealing process, Fig. 7(b) is a diagram for explaining the grinding process, and Fig. 7(c) is a diagram for explaining the wiring layer forming process.
8 is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component) from the laminate 120. Fig. 8(a) is a view showing the laminate 200, Fig. 8(b) is a view for explaining the separation process, and Fig. 8(c) is a view for explaining the adhesive layer removal process.
9 is a graph showing the behavior of the complex elastic modulus with respect to the temperature of the cured body of the adhesive composition to which the present invention is applied.

In the scope of this specification and the claims, "aliphatic" is defined as a relative concept for aromatics, meaning a group, a compound, etc. that does not have aromaticity.

The "alkyl group" is intended to contain a straight chain, branched chain, and cyclic monovalent saturated hydrocarbon group, unless otherwise specified. The alkyl group in the alkoxy group is also the same.

The "alkylene group" is intended to contain a divalent saturated hydrocarbon group of a straight chain, branched chain, and cyclic type, unless otherwise specified.

The "halogenated alkyl group" is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of the hydrogen atoms of the alkyl group or the alkylene group are substituted with fluorine atoms.

"Structural unit" means a monomer unit (monomer unit) constituting a high molecular compound (resin, polymer, copolymer).

When describing "may have a substituent" or "may have a substituent", a hydrogen atom (-H) is substituted with a monovalent group, and a methylene group (-CH ₂ -) is substituted with a divalent group. Includes both.

The term "exposure" is taken as a concept including the overall irradiation of radiation.

The term "constituent unit derived from hydroxystyrene" means a constitutional unit formed by cleavage of the ethylenic double bond of hydroxystyrene. The "constituent unit derived from a hydroxystyrene derivative" means a structural unit formed by cleavage of an ethylenic double bond of a hydroxystyrene derivative.

The term "hydroxystyrene derivative" refers to a concept in which the hydrogen atom at the α position of hydroxystyrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As their derivatives, the hydrogen atom in the hydroxyl group of the hydroxystyrene which may be substituted with a substituent at the hydrogen atom at the α position is an organic group; The thing in which the substituent other than a hydroxyl group couple|bonded with the benzene ring of the hydroxystyrene which the hydrogen atom of the alpha position may be substituted with the substituent is mentioned. Note that the α position (the carbon atom at the α position) refers to a carbon atom to which the benzene ring is bonded, unless otherwise specified.

As a substituent which substitutes the hydrogen atom of the alpha position of hydroxystyrene, the thing similar to what was illustrated as the substituent of the alpha position in the said alpha substituted acrylic acid ester is mentioned.

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

Moreover, the halogenated alkyl group as a substituent of the α position specifically, a group in which a part or all of the hydrogen atoms of the “alkyl group as a substituent of the α position” 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.

Moreover, the hydroxyalkyl group as a substituent of the alpha position specifically, group which substituted some or all of the hydrogen atom of the said "alkyl group as a substituent of the alpha position" with a hydroxyl group is mentioned. 1-5 are preferable and, as for the number of hydroxyl groups in the hydroxyalkyl group, 1 is the most preferable.

In the present specification and the scope of the claims, depending on the structure represented by the formula, there may be a sub-carbon, and there may be an enantiomer or a diastereomer, but in that case, one formula It is represented by representing isomers. These isomers may be used alone or as a mixture.

(Adhesive composition)

The adhesive composition according to the first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support, wherein the adhesive composition is cured by forming a crosslinked structure by heat. It is characterized in that adhesion is carried out, and the crosslinked structure is decomposed by acid or alkali, and the adhesive layer is removed during or after the decomposition process.

<object of temporary adhesion>

The adhesive composition according to the present embodiment is used to form an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device to a support. In the present specification, the term "adhesive adhesion" means that the object to be adhered is temporarily adhered (for example, between arbitrary work steps). More specifically, the semiconductor substrate or the electronic device is temporarily adhered to the support and fixed on the support (temporary adhesion) for thinning of the device, conveyance of the semiconductor substrate, mounting on the semiconductor substrate, and the like, and after completion of the process , 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 generally used as a semiconductor substrate. The semiconductor substrate (bare chip) is provided to processes such as thinning and mounting while being supported by the support. A structure such as an integrated circuit or a metal bump may be mounted on the semiconductor substrate.

As a semiconductor substrate, although a silicon wafer substrate is typically mentioned, it 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 term "electronic device" means a member constituting at least a part of an electronic component. The electronic device is not particularly limited, and various mechanical structures or circuits may be formed on the surface of the semiconductor substrate. The electronic device is preferably a composite of a member made of a metal or a semiconductor and a resin sealing or insulating the member. The electronic device may be a redistribution layer, and/or a semiconductor element or other element, which will be described later, sealed or insulated with an encapsulant or an insulating material, and may have a single-layered structure or a multi-layered structure.

≪Support≫

The support is a member supporting a semiconductor substrate or an electronic device. As described later, the support may have a light transmitting property and may be composed of a support base that is a member supporting the semiconductor substrate and a separation layer that is deteriorated by irradiation with light.

<Component to form a crosslinked structure by heat, and the crosslinked structure is decomposed by acid or alkali: (C) component>

The adhesive composition according to the present embodiment forms a crosslinked structure by heat and is cured, thereby forming an adhesive layer between the semiconductor substrate or electronic device and the support, and temporarily adhering the member. In addition, 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 forms a crosslinked structure by heat and is cured, and the crosslinked structure has a property of being decomposed by acid or alkali (hereinafter also referred to as "(C) component"). Contains.

Although it does not specifically limit as such a component, For example, the component which forms a urethane bond by heat is mentioned. Polyisocyanate compound and polyol are mentioned as a component which forms a urethane bond by heat.

≪Polyisocyanate compound: (I) component≫

The adhesive composition of the present embodiment may contain a polyisocyanate compound (hereinafter also referred to as "(I) component") as (C) component. In the present specification, the term "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 polyisocyanate). . The polyisocyanate is not particularly limited, and those generally used for the production of urethane resins can be used without particular limitation.

The blocked polyisocyanate is a compound in which the isocyanate group of the polyisocyanate is blocked by reaction with a blocking agent and inactivated. (I) It is preferable that the blocked polyisocyanate used as a component is an isocyanate group blocked by the thermally dissociable blocking agent. Examples of the thermal dissociation blocking agent include blocking agents such as oxime cores, diketones, phenols, and caprolactams. The blocked polyisocyanate by the thermally dissociable blocking agent is an isocyanate group inert at room temperature, and when heated, the thermally dissociable blocking agent dissociates to regenerate the isocyanate group.

As a specific example of a polyisocyanate, For example, Aliphatic diisocyanate, such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, and lysine diisocyanate; Alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate ; And tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, naphthylene diisocyanate Aromatic diisocyanates such as; And these burette, isocyanurate, and trimethylolpropane adducts etc. are mentioned. As the polyisocyanate, one type may be used alone, or two or more types may be used in combination.

As the polyisocyanate, commercially available ones may be used. Commercially available polyisocyanates include, for example, Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E , Duranate MFA-75B, Duranate MHG-80B, Duranate TUL-100, Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405 -70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (above, trade names, manufactured by Asahi Chemical Chemicals) and the like. These products may be used alone or in combination of two or more.

As a block isocyanate, the compound in which the isocyanate group of the above polyisocyanate was protected by reaction with a blocking agent is mentioned. The blocking agent is not particularly limited as long as it is a compound that generates an isocyanate group by heating at a temperature higher than or equal to the dissociation temperature, although it is stable at room temperature in addition to a thermally dissociative blocking agent, i.e., an isocyanate group.

Specific examples of the blocking agent include, for example, lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam and propiolactam; Oxime compounds such as methyl ethyl ketooxime, methyl isoamyl ketooxime, methyl isobutyl ketooxime, formamide oxime, acetamide oxime, 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; Alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, trimethylolpropane, and 2-ethylhexyl alcohol; Ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; Active methylene compounds such as alkyl malonate, dialkyl malonate, alkyl acetoacetate, and acetyl acetone; And the like. The block agent may be used alone or in combination of two or more.

The blocked polyisocyanate can be produced by reacting a polyisocyanate with a blocking agent. The reaction of the polyisocyanate and the blocking agent is carried out, for example, in a solvent having no active hydrogen (1.4 dioxane, cellosolve acetate, etc.) under heating at about 50 to 100° C., and, if necessary, in the presence of a blocking catalyst. . The use ratio of the polyisocyanate and the blocking agent is not particularly limited, but preferably, the equivalent ratio of the isocyanate group and the blocking agent in the polyisocyanate is 0.95: 1.0 to 1.1: 1.0, and more preferably 1: 1.05 to 1.15. As a blocking catalyst, a well-known thing can be used, For example, metal alcoholate, such as sodium methylate, sodium ethylate, sodium phenolate, potassium methylate; Tetraalkylammonium Hydroxide, such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium; Organic weak acid salts such as acetate, octylate, myristate and benzoate; And alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylic acid and myristic acid; And the like. As the blocking catalyst, one type may be used alone, or two or more types may be used in combination.

As the block polyisocyanate, commercially available ones may be used. 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 Dura Nate E402-B80B (above, a brand name, Asahi Chemical Co., Ltd. product) etc. are mentioned.

As the component (I), a blocked polyisocyanate having an isocyanate group blocked by a heat dissociable blocking agent is preferable.

(I) As a component, you may use individually by 1 type and may use 2 or more types together.

As for content of (I) component in the adhesive composition of this embodiment, 5-50 mass% with respect to the total amount of (C) component is illustrated, and 10-40 mass% is preferable.

≪Polyol: (P) component≫

The adhesive composition of the present embodiment may contain a polyol (hereinafter also referred to as "(P) component") as (C) component. Polyol is a compound having two or more hydroxyl groups (-OH). The polyol is not particularly limited, and those generally used for the production of urethane resins can be used without particular limitation.

As specific examples of the polyol, 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 , Dihydric alcohols such as hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol and bisphenol A; Trihydric alcohols such as glycerin and trimethylolpropane; Tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; Pentahydric alcohols such as xylitol; Hexavalent alcohols such as sorbitol, mannitol, alinitol, iditol, dulcitol, atritol, inositol, and dipentaerythritol; 7-valent alcohols such as perseitol; And 8-valent alcohol such as sucrose; And the like.

In addition, 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 polyhydroxyalkane, a polyurethane polyol , A polyol of a polymer such as castor oil or a mixture thereof (hereinafter referred to as polyol (1)). 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.

[Phenol resin]

The phenol resin may be a novolac type phenol resin or a resor type phenol resin. The novolak-type phenol resin can be obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenols") and aldehydes under an acid catalyst. Resor type phenol resin can be obtained by addition condensation of phenols and aldehydes under an alkali catalyst.

As said phenol, it is phenol, for example; cresols such as m-cresol, p-cresol, and o-cresol; Xylenols, such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkyl phenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol; alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; Arylphenols such as phenylphenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis And polyhydroxyphenols such as (4-hydroxy-3-methylphenyl)fluorene and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamonaldehyde, 4-isopropylbenzaldehyde , 4-isobutyl benzaldehyde, 4-phenyl benzaldehyde, and the like.

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

[Resin containing hydroxystyrene skeleton]

The resin containing the hydroxystyrene skeleton is not particularly limited as long as it has a structural unit derived from hydroxystyrene or a hydroxystyrene derivative. As a specific example of the structural unit derived from hydroxystyrene or a hydroxystyrene derivative, the structural unit represented by the following general formula (a10-1) is mentioned.

[Formula 1]

[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 said formula (a10-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group.

The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched chain alkyl group having 1 to 5 carbon atoms, specifically, 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 having 1 to 5 carbon atoms in R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, 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 from the ease of industrial availability, a hydrogen atom or a methyl group is most preferred.

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

Examples of the divalent linking group in Ya ^x1 include, for example, a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

Divalent hydrocarbon group which may have a substituent:

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

・The aliphatic hydrocarbon group in Ya ^x1

The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually saturated.

Examples of the aliphatic hydrocarbon group include a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

A straight-chain or branched-chain aliphatic hydrocarbon group

The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

As a linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH ₂ -], an ethylene group [-(CH ₂ ) ₂ -], a trimethylene group [-( And CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -], and pentamethylene group [-(CH ₂ ) ₅ -].

The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

As a branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, Alkyl methylene groups such as -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) _2- ; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) alkyl ethylene groups such as ₂ -CH ₂ -; Alkyltrimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -; And an alkylalkylene group such as an alkyltetramethylene group such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, and the like. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

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

An aliphatic hydrocarbon group containing a ring in the structure

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring) which may include a substituent containing a hetero atom in the ring structure, the cyclic aliphatic The group which the hydrocarbon group couple|bonded to the terminal of the linear or branched-chain aliphatic hydrocarbon group, the group etc. which the said cyclic aliphatic hydrocarbon group interposed in the middle of a linear or branched-chain aliphatic hydrocarbon group etc. are mentioned. The thing similar to the above is mentioned as said linear or branched-chain aliphatic hydrocarbon group.

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

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms are removed from monocycloalkane is preferable. As the monocycloalkane, those having 3 to 6 carbon atoms are preferable, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms are removed from polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, And isobornane, tricyclodecane, and tetracyclododecane.

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, ethyl group, propyl group, n-butyl group or 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, or a tert-butoxy group, Time, an ethoxy group is most preferable.

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 a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

The cyclic aliphatic hydrocarbon group may be partially substituted with a substituent containing a hetero atom in a part of the carbon atoms constituting the ring structure. As a substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -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 conjugate system having 4 n + 2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, it is assumed that the carbon number in the substituent is not included in the carbon number. 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 the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic heterocycle, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. A pyridine ring, a thiophene ring, etc. are mentioned specifically, as an aromatic heterocycle.

Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms are removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); A group in which two hydrogen atoms are removed from an aromatic compound (eg, biphenyl, fluorene, etc.) containing two or more aromatic rings; A group in which one of the hydrogen atoms of a group (aryl group or heteroaryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, 1-naph And a group in which one hydrogen atom is further removed from an aryl group in an arylalkyl group such as a tilmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

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

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

As an alkoxy group, a halogen atom, and a halogenated alkyl group as said substituent, what was illustrated as a substituent which substitutes the hydrogen atom which the said cyclic aliphatic hydrocarbon group has is mentioned.

Divalent linking group containing a hetero atom:

When Ya ^x1 is a divalent linking group containing a hetero atom, preferred as the linking group are -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O -, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(= O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(= O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² -or -Y ²¹ -S(=O) A group represented by ₂ -OY ^22- [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m" is an integer from 0 to 3], etc. Can be heard.

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

General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O )-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ₂₂ -or -Y ²¹ -S(=O) ₂ -OY ²² -among, Y ²¹ and Y ²² are each independently It is a divalent hydrocarbon group which may have a substituent, and the thing similar to the (divalent hydrocarbon group which may have a substituent) exemplified in the description as the divalent linking group is mentioned.

As Y ²¹ , a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, and a C1-C5 straight-chain alkylene group is more preferable, and a methylene group or ethylene group is particularly preferable.

As Y ²² , a straight-chain or branched-chain 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.

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

As Ya ^x1 , a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), -C(=O)-NH-, a straight chain or branched chain alkylene group, Or it is preferable that it is a combination of these, and especially, a single bond is more preferable.

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 (n _ax1 + 1) hydrogen atoms removed from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugate system having 4 n + 2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; And aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic heterocycle, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. A pyridine ring, a thiophene ring, etc. are mentioned specifically, as an aromatic heterocycle.

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

Below, the specific example of the structural unit represented by said general formula (a10-1) is shown.

In the following formulae, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[Formula 2]

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

[Other polyols]

As the polyester polyol, for example, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, and other dibasic acids or dialkyl esters thereof or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene Glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene Polyester polyol obtained by ring-opening polymerization of a polyester polyol or polycaprolactone, polyvalerolactone, poly(β-methyl-γ-valerolactone) obtained by reacting glycols such as ether glycol or a mixture thereof Can be heard.

As the polyether polyol, for example, oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin and the like And polyether polyols obtained by polymerizing an amount of polyol as an initiator.

As the polyether ester polyol, for example, polyether obtained by reacting the polyether polyol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or a mixture thereof, or the polyether polyol. And ester polyols.

As a polyester amide polyol, the polyester amide polyol obtained by using the aliphatic diamine which has amino groups, such as ethylene diamine, propylene diamine, and hexamethylene diamine, as a raw material at the time of the said esterification reaction, for example is mentioned.

Examples of the acrylic polyol include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like, or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid and methacrylic acid Or the polyester amide polyol obtained by copolymerizing the ester is mentioned.

As polycarbonate polyol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9 1 such as -nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, or hydrogenated bisphenol A And polycarbonate polyols obtained by reacting a species or two or more kinds of glycols with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and phosgene.

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

The polyurethane polyol is a polyol having one or more urethane bonds in one molecule, for example, polyether polyols having a number average molecular weight of 200 to 20,000, polyester polyols, polyether ester polyols, and polyisocyanates are preferred. The polyurethane polyol obtained by making NCO/OH react less than 1, More preferably, it is 0.9 or less.

Among the above, as the component (P), a phenol resin or a resin containing a hydroxystyrene skeleton is preferable, a novolak resin or a resin containing a hydroxystyrene skeleton is more preferable, and hydroxystyrene or hydroxystyrene Polymers of derivatives are more preferred, and polyhydroxystyrene resins are particularly preferred.

As (P) component, 1 type may be used individually and 2 or more types may be used together. As for content of (P) component in the adhesive composition of this embodiment, 50-95 mass% with respect to the total amount of (C) component is illustrated, and 60-90 mass% is preferable.

It is preferable that the adhesive composition of this embodiment contains the said (I) component and (P) component as (C) component. In this case, the molar ratio (NCO/OH) of the hydroxyl 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 0.1 to 1 It is preferable, and it is more preferable that it is 0.3-0.7.

Moreover, the ratio ((I) component mass: (P) component mass) of the content of the (I) component and the (P) component contained in the adhesive composition of the present embodiment is in the range of 1: 10 to 10: 1 It is preferable, and it is more preferable that it is 2:8-8:2, and it is still more preferable that it is 2:8-5:5.

<Other ingredients>

The adhesive composition of this embodiment may contain other components in addition to the said (C) component, in the range which does not inhibit the effect of this invention. Other components are not particularly limited, and various conventional additives such as a release agent, a plasticizer, an adhesion aid, a stabilizer, a colorant, a surfactant, and a curing reaction accelerator can be used. Moreover, the adhesive may contain a diluting solvent. The diluting solvent may be inert to the component (C), and examples thereof include ester systems such as ethyl acetate and ketone systems such as methyl ethyl ketone, and aromatic hydrocarbon systems such as toluene and xylene.

According to the adhesive composition of this embodiment, when temporarily bonding a semiconductor substrate or an electronic device and a support, a crosslinked structure is formed by heat to cure, thereby forming an adhesive layer, and bonding the semiconductor substrate or electronic device to the support. Since the adhesive layer is formed of an adhesive layer that is cured by forming a crosslinked structure by heat, heat resistance is high and problems such as misalignment or sinking may occur even when high-temperature treatment is performed during processing of a semiconductor substrate or an electronic device. It doesn't happen very well.

On the other hand, the crosslinked structure in the adhesive layer can be decomposed by acid or 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 is separated from the support, the crosslinked structure is decomposed by applying an acid or alkali to the adhesive layer, and the adhesive layer is removed. Thereby, a semiconductor substrate or an electronic device and a support body can be separated easily. In addition, the residue of the adhesive layer attached to the semiconductor substrate or electronic device can be easily removed with acid or alkali.

(Laminate)

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

1 shows an embodiment of the laminate according to the second aspect.

The laminated body 100 shown in FIG. 1 is provided with the support body 12 in which the support body 1 and the separation layer 2 were laminated, the adhesive layer 3, and the semiconductor substrate 4. In the laminate 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 gas 1 and the separation layer 2, but is not limited to this, and may be composed of only the support gas.

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

The laminated body 200 shown in FIG. 2 is a laminated body except that the electronic device 456 which consists of the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 is laminated on the adhesive layer 3 It is the same structure as (100).

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

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

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

The laminated body 400 shown in FIG. 4 is a laminated body except that the electronic device 645 composed of the wiring layer 6, the semiconductor substrate 4, and the encapsulant layer 5 is laminated on the adhesive layer 3 It is the same structure as (100).

<Support>

The support is a member supporting a semiconductor substrate or an electronic device. In the example of FIGS. 1-4, the support body 12 is provided with the support base 1 and the separation layer 2 formed on the support base 1. In the layered product 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 gas 1 becomes the support.

≪Support gas≫

The support base is a member that has light-transmitting properties and supports a semiconductor substrate or an electronic component. In the case of forming the separation layer as shown in Figs. 1 to 4, the supporting base is bonded to the semiconductor substrate or electronic device through the separation layer and the adhesive layer. When the separation layer is not formed, the support base is bonded to the semiconductor substrate or electronic device through the adhesive layer. Therefore, it is preferable that it has the strength required to prevent damage or deformation of the semiconductor substrate at the time of thinning of the device, conveyance of the semiconductor substrate, mounting on the semiconductor substrate, and the like. Moreover, when a support body has a separation layer, it is preferable that a support gas transmits the light of the wavelength which can denature the separation layer.

As a material of the supporting base, glass, silicone, acrylic resin, or the like is used, for example. Examples of the shape of the support base include a square, a circular shape, and the like, but are not limited to this. Further, as the support gas, for further high-density integration and improvement of production efficiency, a large size of a circular support gas may be used, or a large-sized panel having a rectangular shape when viewed from a plane may be used.

≪Separation layer≫

The separation layer is a layer that is adjacent to the adhesive layer, is denatured by irradiation of light, and is capable of separating a supporting gas from a semiconductor substrate or electronic device fixed to the support through the adhesive layer.

This separation layer can be formed using a composition for forming a separation layer, which will be described later, and is formed, for example, by firing a component contained in the composition for forming a separation layer or by a chemical vapor deposition (CVD) method. The separation layer is preferably deteriorated by absorbing light irradiated through the supporting gas.

The separation layer is preferably formed of only a material that absorbs light, but may be a layer in which a material that does not have a structure that absorbs light is blended in a range that does not impair the essential properties in the present invention.

The thickness of the separation layer is, for example, preferably in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. When the thickness of the separation layer is in the range of 0.05 µm or more and 50 µm or less, desired deterioration can be generated in the separation layer by short-time light irradiation and low-energy light irradiation. Moreover, it is especially preferable that the thickness of the separation layer is within a range of 1 µm or less from the viewpoint of productivity.

It is preferable that the separation layer has a flat surface (not formed with irregularities) on the side in contact with the adhesive layer, whereby the formation of the adhesive layer is easily performed, and the semiconductor substrate or electronic device and the supporting base are uniformly attached ( It is easy to do it.

·Composition for forming a separation layer

The composition for forming the separation layer, which is a material for forming the separation layer, includes, for example, a fluorocarbon, a polymer having a repeating unit including a structure having light absorption properties, an inorganic material, a compound having an infrared absorption structure, infrared absorption What contains a substance, a reactive polysilsesquioxane, or the resin component which has a phenol skeleton is mentioned.

In addition, the composition for forming the separation layer includes, as optional components, fillers, plasticizers, thermal acid generator components, photoacid generator components, organic solvent components, surfactants, sensitizers, or components capable of improving the separation properties of the support gas, etc. It may contain.

Fluorocarbon

The separation layer may contain fluorocarbon. The separation layer composed of fluorocarbons is deteriorated by absorbing light, and as a result, loses strength or adhesion before being irradiated with light. Therefore, by applying a small external force (for example, lifting the support, etc.), the separation layer is broken, making it easy to separate the support from the semiconductor substrate or electronic device. The fluorocarbon constituting the separation layer can be preferably formed by plasma CVD.

Fluorocarbon absorbs light having a wavelength in its own range depending on the type. By irradiating the separation layer with light having a wavelength in a range absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be preferably denatured. It is preferable that the absorption rate of light in the separation layer is 80% or more.

As the light irradiated to the separation layer, for example, a solid 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 the fluorocarbon can absorb. Liquid lasers, CO ₂ lasers, excimer lasers, Ar lasers, gas lasers such as He-Ne lasers, laser beams such as semiconductor lasers, free electron lasers, or non-laser light may be used as appropriate. As the wavelength that can denature the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

A polymer having repeating units containing a structure having light absorption properties

The separation layer may contain a polymer having a repeating unit containing a structure having light absorbing properties. The polymer is deteriorated upon irradiation with light.

Examples of the structure having light absorbing property include an atomic group containing a conjugated π electron system composed of a substituted or unsubstituted benzene ring, a condensed ring, or a heterocyclic ring. More specifically, the structure having light absorption properties is a cardo structure, a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenylsulfone structure), and a diphenyl structure present in the side chain of the polymer. Or a diphenylamine structure is mentioned.

The structure having the above-described light absorbing property can absorb light having a wavelength in a desired range depending on the type. For example, the wavelength of light absorbable by the structure having the above-described light absorbing 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-described light absorbing property is, for example, a high pressure mercury lamp (wavelength 254 nm or more, 436 nm or less), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), Light emitted from an F ₂ excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), 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).

··Inorganic

The separation layer may be made of an inorganic material. As long as this inorganic substance is made to be denatured by absorbing light, for example, one or more kinds selected from the group consisting of metals, metal compounds, and carbons are preferably mentioned. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.

Examples of the 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.

In addition, carbon is a concept in which an allotrope of carbon can be included, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.

The inorganic material absorbs light having a wavelength in its own range depending on the type.

As the light irradiated to the separation layer made of an inorganic substance, depending on the wavelength that the inorganic substance can absorb, 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, and a dye laser Liquid lasers such as CO ₂ lasers, excimer lasers, Ar lasers, gas lasers such as He-Ne lasers, laser beams such as semiconductor lasers and free electron lasers, or non-laser light may be used as appropriate.

The separation layer made of an inorganic material may be formed on a supporting gas by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating, and the like.

A compound having an infrared absorbent structure

The separation layer may contain a compound having an infrared absorbing structure. The compound having the infrared absorbing structure is deteriorated by absorbing infrared light.

Structures having infrared absorption properties or compounds having such structures include, for example, alkanes, alkenes (vinyl, trans, cis, vinylidene, 3 substitution, 4 substitution, conjugated, cumulene, cyclic), alkynes ( 1 substituted, 2 substituted), monocyclic aromatic (benzene, 1 substituted, 2 substituted, 3 substituted), alcohol 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-diketone enol , o-hydroxyaryl ketone, dialkylaldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chlorides, aromatic acid chlorides, acid anhydrides (conjugated, non-conjugated, cyclic, non-cyclic), primary amides, secondary amides, lactams, primary amines (aliphatic, aromatic), Secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide , Aliphatic isonitrile, aromatic isonitrile, isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosoamine, nitric acid ester , Nitrite esters, nitroso bonds (aliphatic, aromatic, monomeric, dimer), sulfur compounds such as mercaptan or thiophenol or thiol acid, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary sulfonamides, agents Secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² bond (A ² is H, C or O) or Ti-O Can be combined have.

Examples of the structure including the carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , aryl fluoride or aryl chloride.

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

As the structure containing the PA ² bond, for example, PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is an aliphatic group or aromatic Group), (A ⁴ O) ₃ -PO (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH or O=P-OH, etc. Can be lifted.

As the compound containing the Ti-O bond, for example, (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium or titanium- alkoxy titanium such as i-propoxy octylene glycolate; (ii) chelate titanium such as di-i-propoxy bis (acetylacetonato) titanium or propane dioxy titanium bis (ethyl acetoacetate); (iii) iC ₃ H ₇ O-[-Ti(OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ or nC ₄ H ₉ O-[-Ti(OnC ₄ H ₉ ) ₂ -O-] titanium polymers such as _n- nC ₄ H ₉ ; (iv) acylates such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate or (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium Titanium; and (v) water-soluble titanium compounds such as di-n-butoxy-bis(triethanol aminato) 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 above-described infrared absorbing structure can absorb infrared rays having a wavelength in a desired range according to the selection of the kind. Specifically, the wavelength of infrared rays capable of absorbing the above-described infrared absorbing structure is, for example, in the range of 1 to 20 μm, and more preferably in the range of 2 to 15 μm.

Moreover, when the said structure is a Si-O bond, a Si-C bond, or a Ti-O bond, it is preferable in the range of 9-11 micrometers.

In addition, the wavelength of infrared rays capable of absorbing 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, BASSLER, and MORRILL, "Identification Method by Spectrum of Organic Compounds (Fifth Edition)-Combination of MS, IR, NMR, and UV" (1992) Year publication). See description on pages 146 to 151.

As a compound having an infrared absorbing structure used for the formation of the separation layer, among the compounds having a structure as described above, it can be dissolved in a solvent for application and solidified to form a high layer. If there is, it is not particularly limited. However, in order to effectively denature the compound in the separation layer and facilitate separation of the supporting gas and the substrate, the absorption of infrared light in the separation layer is large, that is, the infrared radiation when the separation layer is irradiated with infrared light. It is preferable that the transmittance is low. Specifically, it is preferable that the transmittance of infrared rays in the separation layer is lower than 90%, and it is more preferable that the transmittance of infrared rays is lower than 80%.

··Infrared absorbing material

The separation layer may contain an infrared absorbing material. The infrared absorbing material may be one that is deteriorated 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 its own range depending on the type. By irradiating the separation layer with light having a wavelength in the range absorbed by the infrared absorption material used in the separation layer, the infrared absorption material can be preferably deteriorated.

·Reactive polysilsesquioxane

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

The term "reactive polysilsesquioxane" refers to a polysilsesquioxane having a silanol group or a functional group capable of forming a silanol group by hydrolysis at the end of the polysilsesquioxane skeleton. It is possible to polymerize each other by condensing the silanol group or a functional group capable of forming a silanol group. In addition, when the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, the reactive polysilses having silsesquioxane skeletons such as random structures, basket structures, and ladder structures are used. Quioxane can be employed.

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

When the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferred range, a separation layer that can be preferably denatured is formed by irradiating infrared rays (preferably far infrared rays, more preferably light having a wavelength of 9 to 11 µm). Can.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50000, more preferably 1000 to 10000.

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

Commercially available products that can be used as the reactive polysilsesquioxane include, for example, SR-13, SR-21, SR-23 or SR-33 (trade name) manufactured by Konishi Chemical Industries, Ltd.

· Resin component with 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, thereby increasing photoreactivity.

As used herein, "having a phenol skeleton" 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 1000 to 30,000, more preferably 1500 to 20,000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is less than or equal to the upper limit of the above-mentioned preferred range, the solubility of the composition for forming a separation layer in a solvent becomes high.

In addition, it is assumed that the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography) is used as the molecular weight of the resin component.

As the resin component having a phenol skeleton, for example, novolak-type phenol resin, resor-type phenol resin, hydroxystyrene resin, hydroxyphenylsilsesquioxane resin, hydroxybenzylsilsesquioxane resin, phenol skeleton-containing acrylic And resins. Among these, a novolac-type phenol resin and a resor-type phenol resin are more preferable.

<Adhesive layer>

The adhesive layer is formed to temporarily adhere the semiconductor substrate or electronic device to the support. The adhesive layer is a cured body of the adhesive composition according to the first embodiment. More specifically, the adhesive layer is formed by 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, and more preferably in the range of 5 μm or more and 150 μm or less.

Moreover, although the adhesive layer of this embodiment is a hardened|cured material of an adhesive composition as mentioned above, it is preferable that the material (hardened body) which comprises this adhesive layer satisfies the following characteristics.

That is, when the complex elastic modulus of the cured body is measured under the following conditions, the complex elastic modulus at 50°C is preferably 1.0 × 10 ⁸ MPa or more, more preferably 5.0 × 10 ⁸ MPa or more, and more preferably 1.0 × 10 ⁹ MPa or more It is more preferable. The upper limit of the complex elastic modulus at 50°C is, for example, 1.0×10 ¹⁰ MPa or less.

In addition, when measuring the complex elastic modulus of the cured product under the following conditions, that the complex elastic modulus at 200 ℃ less than 1.0 × 10 ⁴ ㎩ are preferred, more preferably not less than ^{5.0 × 10 4 ㎩, 1.0 ×} 10 5 ㎩ or more It is more preferable. The upper limit of the complex modulus at 200°C is, for example, 1.0×10 ⁸ or less.

In addition, the complex elastic modulus of a hardened|cured material can be measured using the dynamic viscoelasticity measuring apparatus Rheogel-E4000 (made by UMB Corporation). Specifically, the adhesive composition was applied onto a PET film with a release agent, and heated by an oven under atmospheric pressure at 90° C. for 5 minutes, and then at 200° C. for 60 minutes to form a test piece having a thickness of 20 μm, and thereafter, The test piece (size 0.5 cm × 1 cm, thickness 20 µm) peeled from the PET film can be measured using the measuring device described above.

Moreover, as the measurement condition, in the tension condition of a frequency of 1 kHz, the conditions of raising the temperature from the starting temperature of 40°C to 240°C at a heating rate of 5°C/min may be employed.

<Semiconductor substrate or electronic device>

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

≪Semiconductor substrate≫

There is no restriction|limiting in particular as a semiconductor substrate, The thing similar to what was exemplified by said "(adhesive composition)" is illustrated. The semiconductor substrate may be a semiconductor element or other elements, and may have a single-layered structure or a multi-layered structure.

≪Electronic device≫

There is no restriction|limiting in particular as an electronic device, The thing similar to what was illustrated in the said "(adhesive composition)" is illustrated. It is preferable that the electronic device is a composite of a member made of a metal or a semiconductor and a resin sealing or insulating the member. Specifically, the electronic device includes at least one of the encapsulant layer and the wiring layer, and may further include a semiconductor substrate.

In the laminate 200 shown in FIG. 2, the electronic device 456 is formed of a semiconductor substrate 4, a sealing material layer 5, and a wiring layer 6. In the layered product 300 shown in FIG. 3, the electronic device 6 is formed of a wiring layer 6. In the layered product 400 shown in FIG. 4, the electronic device 645 is composed of a wiring layer 6, a semiconductor substrate 4, and a sealing material layer 5.

[Encapsulation layer]

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

As a sealing material, a resin composition can be used, for example. The encapsulant layer 5 is not formed for each individual semiconductor substrate 4, but is preferably formed so as to cover the entirety of the semiconductor substrate 4 on the adhesive layer 3. The resin used for the encapsulant is not particularly limited as long as it can encapsulate and/or insulate a metal or semiconductor, and examples thereof include an epoxy resin or a silicone resin. The sealing material may contain other components, such as a filler, in addition to resin. As a filler, spherical silica particles etc. are mentioned, for example.

≪Wiring layer≫

The wiring layer is also referred to as a redistribution layer (RDL), and is a thin film wiring body constituting wiring to be connected to a substrate, and may have a single-layer or multiple-layer structure. The wiring layer is made of a conductor (for example, a metal such as aluminum, copper, titanium, nickel, gold and silver, and a silver-tin alloy) between a dielectric material (such as silicon oxide (SiO _x ) and a photosensitive resin such as photosensitive epoxy). Alloy) may be formed, but is not limited to this.

In addition, in the laminated body of FIGS. 1-4, although the support base 1 and the separation layer 2 are adjacent, it is not limited to this, The other layer between the support base 1 and the separation layer 2 is It may be further formed. In this case, the other layer may be made of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts desirable properties and the like to the laminates 100 to 400 without interfering with the incident of light to the separation layer 2. The wavelength of light that can be used differs depending on the kind of material constituting the separation layer 2. Therefore, the material constituting the other layers does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths capable of deteriorating the material constituting the separation layer 2.

(Method of manufacturing a laminate (1))

The method for producing a laminate according to the third aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer and a semiconductor substrate are stacked in this order, wherein the adhesive composition according to the first aspect is applied to the support or semiconductor substrate. The adhesive composition is formed by applying an adhesive composition layer forming step of applying to form an adhesive composition layer, a semiconductor substrate placing step of placing the semiconductor substrate on the support through the adhesive composition layer, and heating the adhesive composition layer. It is characterized by having an adhesive layer forming step of forming an adhesive layer by curing by forming a crosslinked structure in the layer.

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

5(a) to 5(c) are views for explaining the manufacturing process of the laminate 100' in which the support 12, the adhesive composition layer 3', and the semiconductor substrate 4 are laminated in this order. . 5(a) is a view showing the support 12. The support 12 is composed of a support gas 1 and a separation layer 2. 5(b) is a view for explaining the adhesive composition layer forming step. 5(c) is a view for explaining the semiconductor substrate placement process.

It is a figure explaining an adhesive layer formation process. The adhesive composition layer 3'in the layered product 100' is thermally cured to form the adhesive layer 3, thereby obtaining a layered product 100.

[Adhesive composition layer formation process]

The manufacturing method of the laminated body which concerns on this embodiment contains the adhesive composition layer formation process. The adhesive composition layer forming step is a step of applying an adhesive composition to a support or semiconductor substrate to form an adhesive composition layer. When the support has a separation layer, the adhesive composition layer is formed on the side of the support having the separation layer.

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

The method of forming the adhesive composition layer 3'on the support 12 is not particularly limited, 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.

After forming the adhesive composition layer, a baking treatment may be performed. The baking temperature condition is set to a temperature lower than the heating temperature in the adhesive layer forming process described later. As baking conditions, although it can change according to the kind of (C) component contained in an adhesive composition, for example, 1 to 10 minutes etc. are mentioned under temperature conditions of 70-100 degreeC.

[Semiconductor substrate placement process]

The method for manufacturing a laminate according to the present embodiment includes a semiconductor substrate placement process. The semiconductor substrate placing step is a step of placing the semiconductor substrate on the support through the adhesive composition layer. Thereby, the laminated body 100' can be obtained.

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

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

[Adhesive layer formation process]

The manufacturing method of the laminated body which concerns on this embodiment contains the adhesive layer formation process. The adhesive layer forming step is a step of heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer to cure, thereby forming an adhesive layer. 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 depending on the heat curing temperature of the component (C) contained in the adhesive composition used for forming the adhesive composition layer 3'. For example, when (C) component contains (I) component and (P) component, heating temperature can be made more than the temperature at which the crosslinking reaction of the said (I) component and (P) component starts. For example, when the component (I) contains a blocked polyisocyanate, the heating temperature in this step can be set to a temperature equal to or higher than the dissociation temperature of the thermally dissociable blocking agent blocking the isocyanate group in the blocked polyisocyanate. . The heating temperature may vary depending on the type of the thermally dissociable 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, and from the viewpoint of energy consumption, for example, 350°C or less, 300°C or less, or 250°C or less may be mentioned. As a range of heating temperature, 80-350 degreeC, 100-300 degreeC, 130-300 degreeC, 150-300 degreeC etc. are mentioned, for example.

The heating time is not particularly limited as long as it is a time sufficient for thermal curing of the component (C), but can be, for example, 15 minutes or longer, 30 minutes or longer, or 45 minutes or longer. The upper limit of the heating time is not particularly limited, and can 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. As a range of heating time, 15-120 minutes, 30-120 minutes, 45-120 minutes etc. are mentioned, for example.

By this step, the component (C) in the adhesive composition layer 3'forms a crosslinked structure to cure, thereby forming an adhesive layer 3 that is a cured product of the adhesive composition layer 3'. Thereby, the support body 12 and the semiconductor substrate 4 are temporarily adhered. As a result, the laminate 100 can be obtained.

[Random process]

The method for producing a laminate according to the present embodiment may include other steps in addition to the above steps. Other processes include, for example, a separation layer forming process, and various mechanical or chemical treatments (thinning treatments such as gliding or chemical mechanical polishing (CMP), chemical vapor deposition (CVD) or physical vapor deposition (PVD)). And treatments under high temperature and vacuum, treatments with chemicals such as organic solvents, acidic treatment liquids and basic treatment liquids, plating treatments, irradiation with active light, heating and cooling treatments, and the like.

·Separation layer formation process

When a support body contains a separation layer, the manufacturing method of the laminated body which concerns on this embodiment may include the separation layer formation process. The separation layer forming step is a step of forming a separation layer using a composition for forming a separation layer on one side of a support gas phase.

In Fig. 5(a), a separation layer 2 is formed on the supporting gas 1 by using a composition for forming a separation layer (containing fluorocarbon) (i.e., a supporting gas with a separation layer is provided). Is manufactured).

The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, but, for example, methods such as spin coating, dipping, roller blades, spray coating, slit coating, chemical vapor deposition (CVD), etc. Can be heard.

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 gas 1 under a heating environment or under a reduced pressure environment, or a film is formed or the supporting gas 1 The support 12 can be obtained by forming a film by a vapor deposition method.

(Method for manufacturing a laminate (2))

In the method for producing a laminate according to the fourth aspect of the present invention, after obtaining the laminate by the method for manufacturing the laminate according to the third aspect, a member composed of a metal or a semiconductor and the member sealed or insulated It is characterized by further comprising an electronic device forming process for forming an electronic device, which is a composite of resins.

The laminated body obtained by the manufacturing method of the laminated body of this embodiment is a laminated body in which the support body, an adhesive layer, and an electronic device were laminated in this order. The said laminated body can be obtained by performing an electronic device formation process with respect to the laminated body obtained by the manufacturing method of the laminated body which concerns on the said 3rd aspect.

[Electronic device formation process]

The manufacturing method of the laminated body which concerns on this embodiment contains the electronic device formation process. The electronic device forming process is a process of forming an electronic device, which is a composite of a member composed of a metal or a semiconductor and a resin sealing or insulating the member.

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

·About the encapsulation process

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

In Fig. 7(a), the entirety of the semiconductor substrate 4 temporarily adhered to the support 12 through the adhesive layer 3 is obtained, and the laminate 110 sealed by the sealing material layer 5 is obtained.

In the sealing step, for example, the sealing material heated to 130 to 170° C. is supplied onto the adhesive layer 3 so as to cover the semiconductor substrate 4 while maintaining a high-viscosity state, and is compression molded, whereby the adhesive layer 3 ), a laminate 110 having an encapsulant layer 5 formed thereon 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 encapsulant layer 5 is not formed for each individual semiconductor substrate 4, but is preferably formed so as to cover the entirety of the semiconductor substrate 4 on the adhesive layer 3.

·About the grinding process

The grinding step is a step of grinding the portion of the encapsulant (the encapsulant layer 5) in the encapsulation body so that a part of the semiconductor substrate is exposed after the encapsulation step.

Grinding of the encapsulant portion is performed, for example, by cutting the encapsulant layer 5 to a thickness substantially equal to that of the semiconductor substrate 4, as shown in Fig. 7B.

·Wiring layer formation process

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, a wiring layer 6 is formed on the semiconductor substrate 4 and the encapsulant layer 5. Thereby, the laminated body 120 can be obtained. In the laminate 120, the semiconductor substrate 4, the encapsulant layer 5, and the wiring layer 6 constitute the electronic device 456.

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

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

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

In the method for manufacturing a laminate according to the present embodiment, it is possible to further form bumps or mount elements on the wiring layer 6. The element can be mounted on the wiring layer 6 using, for example, a chip mounter or the like.

(Method for manufacturing a laminate (3))

The method for producing a laminate according to the fifth aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer and an electronic device are laminated in this order, by applying the adhesive composition according to the first aspect on the support, An electronic device that forms on the adhesive composition layer an electronic device that is a composite of an adhesive composition layer forming process for forming a layer of the adhesive composition, a member composed of a metal or a semiconductor, and a resin sealing or insulating the member. It is characterized in that it has a forming step and an adhesive layer forming step of heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer to cure, thereby forming an adhesive layer.

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

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

In the manufacturing method of this embodiment, an electronic device formation process is performed after an adhesive composition layer formation process. As such an electronic device forming process, a wiring layer forming process may be included. The electronic device forming process may further include a semiconductor substrate placement process, a sealing process, and a grinding process. Moreover, the electronic device forming process may be a process in which the semiconductor substrate is placed on a support through an adhesive composition layer through a sealing body sealed with a sealing material.

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

After the adhesive layer forming step, if necessary, an electronic device forming step may be performed. The electronic device forming process may include, for example, a semiconductor substrate placement process, an encapsulation process, and a grinding process.

According to the manufacturing method of the laminate according to the third to fifth aspects, since the support, the semiconductor substrate or the electronic device is temporarily adhered through the adhesive layer having high heat resistance, the support, the adhesive layer, the semiconductor substrate or the electronic device are A laminate formed in order can be stably manufactured. Such a laminate is a laminate manufactured in a process based on a fan-out technique in which terminals formed on a semiconductor substrate are mounted on a wiring layer that extends out of the chip area.

(Method of manufacturing electronic components)

In the method for producing an electronic component according to the sixth aspect of the present invention, after obtaining the laminate by the method for producing a laminate according to any of the third to fifth aspects, the crosslinked structure in the adhesive layer is added to an acid or alkali. It is characterized in that it has an adhesive layer removing step of dissolving and removing the adhesive layer.

When the support body is composed of a supporting gas and a separation layer, the method according to the present embodiment is to irradiate light to the separation layer through the supporting gas and denature the separation layer before the adhesive layer removal process, Alternatively, a separation step for separating the supporting gas may be further included.

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

[Separation process]

When a support body has a separation layer, the manufacturing method of the electronic component which concerns on this embodiment may have a separation process. In the separation process in the present embodiment, light (arrows) is irradiated to the separation layer 2 through the supporting gas 1, and the separation layer 2 is denatured, thereby supporting the supporting gas 1 from the electronic device 456. ).

As shown in Fig. 8(a), in the separation step, the separation layer 2 is denatured by irradiating the separation layer 2 with light (arrows) through the supporting gas 1.

As a wavelength which can denature the separation layer 2, the range of 600 nm or less is mentioned, for example.

The type and wavelength of the light to be irradiated may be appropriately selected depending on the transmittance of the supporting gas 1 and the material of the separation layer 2, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser Solid-state laser such as fiber laser, liquid laser such as dye laser, CO ₂ laser, excimer laser, Ar laser, gas laser such as He-Ne laser, semiconductor laser, laser light such as free electron laser, non-laser light are available Can. Thereby, the separation layer 2 is denatured, and the support gas 1 and the electronic device 456 can be easily separated.

When irradiating laser light, the following conditions are mentioned as an example of the laser light irradiation conditions.

The average output value of the laser light is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser light is preferably 100 mm/s or more and 10000 mm/s or less.

After the separation layer 2 is denatured by irradiating the separation layer 2 with light (arrows), the support gas 1 is separated from the electronic device 456 as shown in FIG. 8(b).

For example, the support gas 1 and the electronic device 456 are separated from each other by applying a force in a direction away from each other. Specifically, in the state where one of the supporting gas 1 or the electronic device 456 side (wiring layer 6) is fixed to the stage, the other is adsorbed and held by a separation plate provided with an adsorption pad such as a bellows pad. By lifting while, the support gas 1 and the electronic device 456 can be separated.

The force exerted on the laminate 200 may be appropriately adjusted depending on the size of the laminate 200 and the like, but is not limited thereto. For example, if the laminate is about 300 mm in diameter, 0.1 to 5 kgf (0.98) -49 N), the support gas 1 and the electronic device 456 can be preferably separated.

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

[Adhesive layer removal process]

The manufacturing method of the electronic component which concerns on this embodiment has an adhesive layer removal process. The adhesive layer removal step is a step of decomposing the crosslinked structure in the adhesive layer with acid or alkali to remove the adhesive layer.

In FIG. 8( b), after the separation step, the adhesive layer 3 and the separation layer 2 are attached to the electronic device 456. In this step, the adhesive layer 3 and the separation layer 2 are removed by using the acid or alkali to decompose the adhesive layer 3 to obtain the electronic component 50.

In this step, the acid or alkali used to decompose 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 constituted by a urethane bond, an acid or alkali capable of decomposing the urethane bond may be used. Examples of the acid capable of decomposing the urethane bond include hydrochloric acid, sulfuric acid, and nitric acid, but are not limited thereto. Moreover, as an alkali which can decompose a urethane bond, inorganic bases, such as potassium hydroxide and sodium hydroxide; And organic amines such as tetramethylammonium hydroxide and monoethanolamine, but are not limited thereto.

The above acid or alkali is dissolved in a solvent and can be used as a treatment liquid for removing the adhesive layer. The solvent is preferably a polar solvent, for example, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol or ethylene glycol, propylene glycol, etc. Can be lifted.

The said adhesive removal processing liquid may contain a well-known additive, such as surfactant, in addition to the said component.

Although it does not specifically limit as content of acid or alkali in the said processing liquid, For example, 1-50 mass% is mentioned. Moreover, 50-99 mass% is mentioned as content of the polar solvent in the said treatment liquid.

By bringing the above 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 manufacturing method of the electronic component according to the present embodiment, a semiconductor substrate or electronic device and a support are formed using an adhesive composition in which a crosslinked structure is cured by heat, and the crosslinked structure is decomposed by acid or alkali. Because of the temporary adhesion, 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. Moreover, since the crosslinked structure in the said adhesive layer is decomposed|disassembled by an acid or an alkali, the cleaning and removal of the adhesive layer after the electronic device formation process etc. are completed can be performed easily.

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

Example

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

<Preparation of adhesive composition>

(Examples 1 and 2)

The components shown in Table 1 were mixed, and the adhesive composition of each example was prepared, respectively.

In Table 1, each symbol has the following meaning. The value in [] is the compounding quantity (part by mass).

(P)-1: Novolak type phenolic resin (MEHC-7841-3H (trade name), manufactured by Meiwa Chemical 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 Chemical Co., Ltd.).

(Ad)-1: Surfactant (BYK0310 (trade name), manufactured by BYK).

<Evaluation>

≪Heat resistance≫

Evaluation of heat resistance was performed by measuring the complex elastic modulus of the cured body of the adhesive composition.

The adhesive composition of each example was applied onto a PET film with a release agent, and heated by 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 of 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 UMB Corporation).

The measurement conditions were set to a condition of increasing the temperature from a starting temperature of 40°C to 240°C at a heating rate of 5°C/min under tensile conditions of a frequency of 1 kHz.

9 is a graph showing the behavior of the complex elastic modulus with respect to temperature for a 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 high complex modulus of elasticity in a substantially constant range in a high-temperature portion (about 150°C or higher).

≪Removability≫

On the glass support substrate (size diameter 30 cm, thickness 1000 µm), each of the adhesive compositions of each example was applied while rotating at 1000 rpm by a spin coat method. Subsequently, an adhesive layer having a thickness of 50 µm was formed by heating the supporting gas to which the adhesive composition of each example was applied, respectively, at 90°C for 5 minutes and at 200°C for 60 minutes.

The adhesive layer of each example was a mixed solvent of N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) in a treatment solution (tetramethylammonium hydroxide (TMAH)) at room temperature (23° C.) (NMP: DMS = 50:50 (mass ratio)), and was diluted with a concentration of 2% by mass) to measure the time to completely dissolve. From the dissolution time to the film thickness, the dissolution rate of the adhesive layer in each example was calculated. Table 2 shows the results.

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 can be easily removed using the treatment liquid.

1 support gas
2 separation layer
3 adhesive layer
3'adhesive composition layer
4 semiconductor substrate
5 Encapsulation layer
6 Wiring layer
10 Middle floor
12 Support
20 laminate
50 electronic components
100 laminate
100' laminate
110 laminate
120 laminate
200 laminate
300 laminate
400 laminate
456 electronic devices
645 electronic devices

Claims (11)

An adhesive composition used to form an adhesive layer for temporarily adhering a semiconductor substrate or an electronic device and a support,
The adhesive composition is cured by forming a crosslinked structure by heat, thereby performing the temporary adhesion,
The crosslinked structure is decomposed by an acid or alkali, and the adhesive layer is removed during or after the process of the decomposition, the adhesive layer. According to claim 1,
The crosslinked structure is formed by urethane bonding, an adhesive composition. According to claim 1,
An adhesive composition comprising a polyisocyanate compound and a polyol. The method of claim 3,
An adhesive composition, characterized in that, as the electronic device, a composite made of a metal or a semiconductor and a resin encapsulating or insulating the member is laminated to the support through the adhesive layer. A laminate in which a support, an adhesive layer, and a semiconductor substrate or electronic device are stacked in this order,
The said adhesive layer is a hardened|cured material of the adhesive composition in any one of Claims 1-4, The laminated body. A method of manufacturing a laminate in which a support, an adhesive layer and a semiconductor substrate 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 to the support or semiconductor substrate to form an adhesive composition layer;
A semiconductor substrate placement process for placing the semiconductor substrate on the support through the adhesive composition layer;
A method for producing a laminate having an adhesive layer forming step of heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer to cure, thereby forming an adhesive layer. An electronic device forming process for forming an electronic device, which is a composite of a member composed of a metal or a semiconductor, and a resin that encapsulates or insulates the member after obtaining the laminate by the method for manufacturing a laminate according to claim 6 A method of manufacturing a laminate having a support, an adhesive layer, and an electronic device further laminated in this order. A method of manufacturing 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 forming a layer of the adhesive composition by applying the adhesive composition according to any one of claims 1 to 4 on the support,
An electronic device forming process of forming an electronic device which is a composite of a member made of a metal or a semiconductor and a resin that encapsulates or insulates the member on the adhesive composition layer,
A method for producing a laminate having an adhesive layer forming step of heating the adhesive composition layer to form a crosslinked structure in the adhesive composition layer to cure, thereby forming an adhesive layer. The method of claim 6,
The support is composed of a support layer and a separation layer that is deteriorated by irradiation of light,
The adhesive composition layer forming step is a step of forming an adhesive composition layer on the separation layer, a method for producing a laminate. After obtaining a laminated body by the manufacturing method of the laminated body of Claim 6,
A method of manufacturing an electronic component having an adhesive layer removing step of decomposing the crosslinked structure in the adhesive layer with acid or alkali to remove the adhesive layer. After obtaining a laminated body by the manufacturing method of the laminated body of Claim 9,
A separation step of separating the electronic device and the support gas by irradiating light to the separation layer through the support gas and changing the separation layer;
After the separation step, the crosslinked structure in the adhesive layer is decomposed by acid or alkali, and an adhesive layer removal step of removing the adhesive layer attached to the electronic device, the electronic component manufacturing method.

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