JP6842878B2 - Adhesive composition and its use - Google Patents

Description

The present invention relates to an adhesive composition and its use.

As a semiconductor package (semiconductor device) including a semiconductor element (electronic component), WLP (Wafer Level Package), PLP (Panel Level Package) and the like are known. For semiconductor packages such as WLP and PLP, fan-in type technology such as fan-in type WLP (Fan-in Wafer Level Package) that rearranges the terminals at the end of the bare chip in the chip area and outside the chip area Fan-out type technologies such as fan-out type WLP (Fan-out Wafer Level Package) for rearranging terminals are known. In particular, the fan-out type technology has been applied to a fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged and packaged on a panel, and semiconductor devices are integrated, thinned, and miniaturized. Fan-out technologies such as these are attracting attention in order to realize this.

Patent Document 1 describes an adhesive composition containing a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer.

Japanese Unexamined Patent Publication No. 2014-105316 (published on June 9, 2014)

However, with the advancement of semiconductor packaging technology for realizing integration, thinning, and miniaturization of semiconductor devices, higher heat resistance and higher chemical resistance than the adhesive composition described in Patent Document 1 have been achieved. There is a demand for a novel adhesive composition capable of forming an adhesive layer having high detergency.

The present invention has been made in view of the above problems, and an object of the present invention is a novel adhesive composition capable of forming an adhesive layer having high heat resistance, high chemical resistance, and high detergency. And its related technology.

In order to solve the above problems, the adhesive composition according to the embodiment of the present invention is used.
An adhesive composition for forming the adhesive layer in a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The glass transition temperature of the adhesive layer is 160 ° C. or higher, and the adhesive layer contains a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher as a resin component.

Alternatively, the adhesive composition according to one embodiment of the present invention may be used.
An adhesive composition for forming the adhesive layer in a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The adhesive layer contains, as a resin component, a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher, and a polyfunctional curable monomer.
The glass transition temperature when the adhesive layer is cured by the polymerization of the polyfunctional curable monomer is 160 ° C. or higher.

The adhesive composition according to the present invention has the effect of being able to provide a novel adhesive composition having high heat resistance, high chemical resistance, and high detergency, and related techniques thereof.

It is a figure explaining the manufacturing method of the laminated body and the substrate processing method which concerns on one Embodiment of this invention. It is a figure explaining the manufacturing method of the laminated body and the substrate processing method which concerns on one Embodiment of this invention. It is a figure explaining the manufacturing method of the laminated body and the substrate processing method which concerns on one Embodiment of this invention. It is a figure explaining the outline of the manufacturing method of the laminated body which concerns on one Embodiment of this invention. It is a figure explaining the outline of the arrangement of the element on the adhesive layer in the evaluation of adaptability to the sealing of an element by a compression type.

Hereinafter, embodiments of the present invention will be described in detail.

<Adhesive Composition (Embodiment 1)>
The adhesive composition according to one embodiment (Embodiment 1) of the present invention is an adhesive composition for forming the adhesive layer in a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order. Therefore, the glass transition temperature of the adhesive layer is 160 ° C. or higher, and the adhesive layer contains a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher as a resin component.

As a known method, the glass transition temperature of the adhesive layer formed by the adhesive composition is, for example, dynamic mechanical analysis (Dynamic Mechanical Analysis), and the temperature is 5 ° C./min under the condition of a frequency of 1 Hz. It can be obtained based on the change in viscoelasticity measured by raising the temperature from 25 ° C. to 300 ° C. at the rate of temperature rise.

Unless otherwise specified, in the present specification, the "resin component" means a cycloolefin polymer and a curable monomer described later.
The adhesive layer formed by using the adhesive composition having the above structure has high heat resistance and high chemical resistance required for forming a sealing substrate (substrate). In addition, it is possible to form an adhesive layer that can suitably remove the residue of the adhesive layer after forming the sealing substrate with a solvent.

The high heat resistance of the adhesive layer formed by the adhesive composition is, for example, (i) that it can be prevented from being deformed when a force is applied in a high temperature environment, (ii). It means that damage such as cracks does not occur when exposed to a high temperature environment for a long time.

[Resin component]
The adhesive composition according to the first embodiment of the present invention has a glass transition temperature of 160 ° C. or higher and contains a cycloolefin polymer as a resin component. By containing a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher, an adhesive layer that can be suitably removed using a solvent while having high heat resistance and high chemical resistance is formed. Can be done.

The glass transition point (Tg) of the cycloolefin polymer is preferably 160 ° C. or higher, more preferably 200 ° C. or higher.

Specific examples of the cycloolefin polymer include a ring-opening polymer of a monomer component containing a cycloolefin monomer, an addition polymer obtained by addition polymerization of a monomer component containing a cycloolefin monomer, and the like.

Examples of the cycloolefin polymer include dicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclics such as tetracyclopentadiene, and pentadiene trimers. Rings, seven-rings such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) and alkenyl (vinyl, etc.) substituents, alkylidene (ethylidene, etc.), aryl (such as ethylidene) substituents of these polycyclics. Examples thereof include polymers having a monomer such as a substituent (phenyl, trill, naphthyl, etc.) as a constituent unit. Among these, a polymer having a monomer having a norbornene structure selected from the group consisting of norbornene, tetracyclododecene, or an alkyl-substituted product thereof as a constituent unit is more preferable. By using such a cycloolefin polymer having a norbornene structure or the like as a constituent unit, for example, an adhesion that can be suitably dissolved and removed by a hydrocarbon solvent while having high chemical resistance to a resist solvent, for example. An adhesive composition capable of forming a layer can be obtained.

The cycloolefin polymer may use another monomer copolymerizable with the above-mentioned cycloolefin-based monomer as a monomer unit, and for example, an alkene monomer is preferably used as a monomer unit. Examples of the alkene monomer include an alkene monomer having 2 to 10 carbon atoms, and examples thereof include α-olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-hexene. Among these, ethylene is a monomer. It is more preferable to use it as a unit. The alkene monomer may be linear or branched.

The ratio of the cycloolefin monomer to the total monomer component constituting the cycloolefin polymer is preferably 10 mol% or more and 100 mol% or less, and more preferably 20 mol% or more and 100 mol% or less.

It should be noted that the polymer having a cycloolefin structure is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin-based monomer and an alkene monomer, at a high temperature. It is preferable in suppressing the generation of gas below.

The polymerization method, polymerization conditions, etc. when polymerizing the monomer component are not particularly limited and may be appropriately set according to a conventional method.

The weight average molecular weight of the cycloolefin polymer is preferably in the range of 10,000 or more and 2,000,000 or less, and more preferably in the range of 30,000 or more and 1,500,000 or less. When the weight average molecular weight of the polymer having a cycloolefin structure is 10,000 or more, the softening temperature of the polymer can be set to a temperature suitable for bonding with glass. When the weight average molecular weight of the polymer having a cycloolefin structure is 2,000,000 or less, the polymer can impart suitable solubility to a washing solution.

Commercially available products that can be used as cycloolefin polymers include, for example, "TOPAS (trade name)" manufactured by Polyplastics Corporation, "APEL (trade name)" manufactured by Mitsui Kagaku Co., Ltd., and "APEL (trade name)" manufactured by Nippon Zeon Co., Ltd. Examples thereof include "ZEONOR (trade name)" and "ZEONEX (trade name)", and "ARTON (trade name)" manufactured by JSR Corporation.

(Thermal polymerization inhibitor)
In the present invention, the adhesive composition may contain a thermal polymerization inhibitor. The thermal polymerization inhibitor has a function of preventing a radical polymerization reaction due to heat or light. Specifically, since the thermal polymerization inhibitor exhibits high reactivity with radicals, it reacts preferentially over cycloolefin polymers to prohibit the polymerization of cycloolefin polymers with each other. Therefore, it is possible to prevent the adhesive layer formed of the cycloolefin polymer from being heated to reduce the solubility of the adhesive layer in the cleaning solution.

The thermal polymerization inhibitor is not particularly limited as long as it is effective in preventing a radical polymerization reaction due to heat, but a thermal polymerization inhibitor having phenol is preferable. As a result, good solubility can be ensured even after high-temperature treatment in the atmosphere. As such a thermal polymerization inhibitor, a hindered phenol-based antioxidant can be used, and for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, etc. Amyroxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene) bis (2-methylphenol), 4,4'-(1-methylethylidene) bis (2,6) -Dimethylphenol), 4,4'-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] tert] bisphenol, 4,4', 4 "-ethylidentris (2-" Methylphenol), 4,4', 4 "-ethylidentrisphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 2,6-di-tert-butyl -4-Methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3) -Methyl-6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl]- 2,4,8,10-Tetraoxaspiro (5,5) undecane, triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, n-octyl-3-3 (3,5-Di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythryltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX1010, BASF) , Tris (3,5-di-tert-butylhydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Only one type of thermal polymerization inhibitor may be used, or two or more types may be used in combination.

The content of the thermal polymerization inhibitor may be appropriately determined according to the type of the cycloolefin polymer, the use of the adhesive composition, and the environment in which it is used. For example, when the amount of the cycloolefin polymer is 100 parts by weight, It is preferably 0.1 parts by weight or more and 10 parts by weight or less. When the content of the thermal polymerization inhibitor is within the above range, the effect of suppressing polymerization is satisfactorily exhibited, and it is possible to further suppress the decrease in solubility of the adhesive composition in the cleaning solution after the high temperature process.

(Additional solvent)
The thermal polymerization inhibitor is preferably dissolved in an additive solvent and blended in the adhesive composition. The additive solvent is not particularly limited, but an organic solvent that dissolves the components contained in the adhesive composition can be used.

As the organic solvent, for example, it is sufficient that each component of the adhesive composition can be dissolved to obtain a uniform solution, and only one organic solvent may be used, or two or more organic solvents may be used in combination. May be good.

Specific examples of the organic solvent include terpene solvents having an oxygen atom, a carbonyl group, an acetoxy group or the like as polar groups, and examples thereof include geraniol, nerol, linalol, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpine-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carboxylic, yonon, tsuyon, Menthol can be mentioned. Also, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol. Polyhydric alcohols such as; monomethyl ethers of compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyhydric alcohols or compounds having the ester bond. , Monoalkyl ethers such as monoethyl ether, monopropyl ether, monobutyl ether, and derivatives of polyhydric alcohols such as compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), (Preferably propylene glycol monomethyl ether (PGME)); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid. Esters such as methyl and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol and butylphenyl ether can be mentioned.

The content of the additive solvent may be appropriately adjusted according to the type of the thermal polymerization inhibitor, etc., but for example, when the total of the diluting solvent (main solvent) for dissolving the resin component and the additive solvent is 100 parts by weight. The content of the additive solvent is preferably 1 part by weight or more and 50 parts by weight or less, and more preferably 1 part by weight or more and 30 parts by weight or less. When the content of the additive solvent is within the above range, the thermal polymerization inhibitor can be sufficiently dissolved.

(solvent)
The solvent (main solvent) contained in the adhesive composition according to the first embodiment of the present invention may be any one having a function of dissolving a cycloolefin polymer, for example, a non-polar hydrocarbon solvent or a polar solvent. And a non-polar petroleum solvent or the like can be used. Preferably, the solution contains an alicyclic hydrocarbon, or a branched hydrocarbon.

Among these, when the solvent contains condensed polycyclic hydrocarbons or branched hydrocarbons, it is possible to avoid the white turbidity that may occur when the adhesive composition is stored in a liquid form (particularly at a low temperature). , It is preferable because it can improve the product stability.

Examples of the hydrocarbon solvent include linear, branched or cyclic hydrocarbons. For example, linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane and tridecane, and branched hydrocarbons having 4 to 15 carbon atoms such as isooctane, isononan and isododecane; p- Saturated aliphatic hydrocarbons such as menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpinene, 1,8-terpinene, bornan, norbornan, pinan, tsujan, karan, longihorene, α-terpinene, β- Examples thereof include terpinene, γ-terpinene, α-pinene, β-pinene, α-tujon, β-tujon and the like.

The petroleum-based solvent is a solvent refined from heavy oil, and examples thereof include white kerosene, paraffin-based solvent, and isoparaffin-based solvent, and may be a mixture of the above-mentioned linear, branched, or cyclic hydrocarbons. .. Further, the petroleum-based solvent may contain, for example, an aromatic compound such as benzene or naphthalene.

The alicyclic hydrocarbon is a hydrocarbon containing a cyclic structure, and examples thereof include cyclohexane, cycloheptane, and cyclooctane.

Moreover, as an alicyclic hydrocarbon, a condensed polycyclic hydrocarbon can be mentioned. A condensed polycyclic hydrocarbon is a hydrocarbon of a fused ring formed by supplying only one side of each ring to each other by two or more monocycles, and is a hydrocarbon obtained by condensing two monocycles. It is preferable to use it.

Such hydrocarbons include combinations of 5-membered and 6-membered rings, or combinations of two 6-membered rings. Examples of hydrocarbons in which a 5-membered ring and a 6-membered ring are combined include indene, pentalene, indane, and tetrahydroindene, and examples of hydrocarbons in which two 6-membered rings are combined include naphthalene and tetrahydronaphthalene (). Tetralin) and decahydronaphthalene (decalin) and the like.

Further, as the branched hydrocarbon, for example, in addition to the above-mentioned isooctane, isononan, isododecane and the like, for example, an isoparaffin-based petroleum solvent such as "Isoper (trade name)" manufactured by ExxonMobil Chemical Co., Ltd. and the like and the like. Can be mentioned.

When the solvent contains the condensed polycyclic hydrocarbon or the branched hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon or the branched hydrocarbon, for example. It may contain other components such as saturated aliphatic hydrocarbons. Further, it may be a combination of a condensed polycyclic hydrocarbon and a branched hydrocarbon, and may contain other components such as a saturated aliphatic hydrocarbon. In this case, the content of the condensed polycyclic hydrocarbon or the branched hydrocarbon is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, with 100 parts by weight of the entire hydrocarbon solvent. .. When the content of the condensed polycyclic hydrocarbon or the branched hydrocarbon is 40 parts by weight or more of the entire hydrocarbon solvent, high solubility in the resin can be exhibited. When the mixing ratio of the condensed polycyclic hydrocarbon or the branched hydrocarbon and the saturated aliphatic hydrocarbon is within the above range, the odor of the condensed polycyclic hydrocarbon or the branched hydrocarbon can be alleviated.

The content of the solvent in the adhesive composition according to the first embodiment of the present invention may be appropriately adjusted according to the thickness of the adhesive layer formed by using the adhesive composition. For example, when the total amount of the adhesive composition is 100 parts by weight, it is preferably in the range of 20 parts by weight or more and 90 parts by weight or less. When the content of the solvent is within the above range, the viscosity can be easily adjusted.

<Adhesive Composition (Embodiment 2)>
The adhesive composition according to the present invention is not limited to the above embodiment (Embodiment 1). For example, the adhesive composition according to another embodiment (Embodiment 2) is an adhesive composition for forming the adhesive layer in a laminate in which a substrate, an adhesive layer, and a support are laminated in this order. The adhesive layer contains a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher and a polyfunctional curable monomer as a resin component, and the polyfunctional curable monomer is polymerized. Therefore, when the adhesive layer is cured, the glass transition temperature of the adhesive layer is 160 ° C. or higher.

Similar to the first embodiment, the adhesive composition having the above structure also has high heat resistance and high chemical resistance required for forming a sealing substrate (substrate), and is suitably suitable for a solvent. An adhesive layer that can be removed can be formed.

In addition, the adhesive composition according to the present embodiment contains a solvent and an additive solvent, similarly to the adhesive composition according to the above embodiment (Embodiment 1). The solvent may be any solvent that can dissolve the cycloolefin polymer and the curable monomer, and for example, the solvent described in the above (solvent) column can be used.

[Resin component]
The adhesive composition according to the present embodiment contains a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher and a curable monomer as a resin component.

As the cycloolefin polymer, a cycloolefin polymer containing the same monomer components as the cycloolefin polymer described in the above-described embodiment (Embodiment 1) can be used. Further, in the adhesive composition according to the present embodiment, the glass transition temperature of the cycloolefin polymer is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and most preferably 140 ° C. or higher. .. Therefore, as in the above-described embodiment (Embodiment 1), a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher can also be used. When the glass transition temperature of the cycloolefin polymer is 100 ° C. or higher, the glass transition temperature is 160 ° C. or higher by polymerizing the polyfunctional curable monomer in a state of being blended with the cycloolefin polymer. The layer can be suitably formed.

(Polyfunctional curable monomer)
The adhesive composition according to the present embodiment contains a polyfunctional curable monomer compatible with the cycloolefin polymer as a resin component. As a result, an adhesive layer having a glass transition temperature of 160 ° C. or higher can be formed by polymerizing a curable monomer using a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher. The curable monomer is preferably a monomer that is polymerized by a radical polymerization reaction, and typically includes a polyfunctional (meth) acrylate monomer.

Examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth). Meta) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecandy Methanoldi (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A di (meth) acrylate, 1,3-adamantandiol di (meth) acrylate , 5-Hydroxy-1,3-adamantandiol di (meth) acrylate, 1,3,5-adamantan trioltri (meth) acrylate, trimethylpropanthry (meth) acrylate, glycerindi (meth) acrylate, pentaerythritoldi (Meta) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxy Propyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin tri (meth) acrylate, glycerin polyglycidyl ether poly Examples thereof include (meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), and a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

The curable monomer preferably has a cyclic structure, and more preferably has a polycyclic aliphatic structure. When the curable monomer has a cyclic structure, more preferably a polycyclic aliphatic structure, compatibility with the cycloolefin polymer can be enhanced. Further, the heat resistance of the adhesive layer can be further enhanced by polymerizing the curable monomer blended in the cycloolefin polymer.

Therefore, among the above (meth) acrylate monomers, a (meth) acrylate monomer having a cyclic group is particularly preferable, and tricyclodecanedimethanol di (meth) acrylate, 1,3-adamantandiol di (meth) acrylate, 5-. Hydroxy-1,3-adamantandiol di (meth) acrylate, 1,3,5-adamantan trioltri (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 9,9-bis [4-( At least one selected from the group consisting of 2- (meth) acryloyloxyethoxy) phenyl] fluorene and propoxylated bisphenol A di (meth) acrylate is more preferable. Among these, a monomer having an adamantane skeleton is particularly preferable because it can increase the heat resistance of the adhesive layer.

The content of the curable monomer may be determined in consideration of the glass transition temperature of the cycloolefin polymer. For example, if the glass transition temperature of the cycloolefin polymer contained as a resin component in the adhesive composition is 100 ° C. or higher, the content of the curable monomer is 10% by weight or more, assuming that the total of the resin components is 100% by weight. , It is preferably in the range of 40% by weight or less. When the content of the curable monomer is 10% by weight or more with respect to the resin component, higher heat resistance can be imparted to the adhesive layer. Further, when the content of the curable monomer is 40% by weight or less, the detergency when the adhesive layer is removed by the cleaning liquid can be improved. In other words, by using a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher, the content of the curable monomer can be reduced to 40% by weight or less, whereby the curable monomer is cured and the adhesive layer is formed. It is possible to prevent the cleaning property of the polymer from being lowered. Therefore, the more the cycloolefin polymer having a higher glass transition temperature is used, the smaller the content of the curable monomer can be.

(Polymerization initiator)
The adhesive composition according to the present embodiment further contains a polymerization initiator that promotes the polymerization reaction of the curable monomer.

The polymerization initiator is not particularly limited as long as it can accelerate the polymerization reaction of the curable monomer, and a thermal polymerization initiator, a photopolymerization initiator and the like can be used. Examples of the thermal polymerization initiator include peroxides and azo-based polymerization initiators.

Examples of the peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters and the like. Specifically, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-Chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl-2-methylpropyl-1 -Hydroperoxide, pertriphenylacetate-tert-butyl, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, 4-methoxyacetic acid per-methoxy. Examples thereof include tert-butyl and tert-butyl peroxide (3-toluyl) carbamate.

Examples of commercially available peroxides include the product name "Park Mill (registered trademark)", the product name "Perbutyl (registered trademark)", the product name "Parloyl (registered trademark)", and products manufactured by Nippon Oil & Fats Co., Ltd. Examples include the name "Perocta (registered trademark)".

Examples of the azo polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl) diacetate, 2, 2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyamide, 2,2' -Azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate methyl, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, Dimethyl 2,2'-azobisisobutyate, 1,1'-azobis (1-methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile 4,4' -Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanovaleronitrile Dimethyl, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobiscyclohexanenitrile , 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis-1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cyclo Heptannitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobisisobutymen, 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane , 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyanopentanoate), poly (tetraethylene glycol-2,2'-azobisisobuty Rate) and the like.

(Photopolymerization initiator)
Specific examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl. ] -2-Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) ) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone 1- [9-ethyl-6- () 2-Methylbenzoyl) -9H-carbazole-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethyl Amino benzoic acid, methyl 4-dimethylamino benzoate, ethyl 4-dimethylamino benzoate, butyl 4-dimethylamino benzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, Benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chloro Thioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumempaoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-) Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Body, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethylmihi) Larsketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin -T-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt -Butyltrichloroacetophenone, pt-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9- Phenylacridin, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4 , 6-Tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4 , 6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4- (4-) Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- Examples thereof include trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. Be done. In addition, as photopolymerization initiators, commercially available products "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade names: all manufactured by BASF) and "NCI-" 831 ”(trade name: manufactured by ADEKA Corporation) and the like can also be used.

The blending amount of the polymerization initiator may be adjusted according to the content of the curable monomer contained in the adhesive composition. Here, the ratio of the polymerization initiator to 100 parts by weight of the curable monomer is preferably 0.1 parts by weight or more and 10 parts by weight or less, and preferably 0.5 parts by weight or more and 5 parts by weight or less. More preferred.

The polymerization initiator can be blended into the adhesive composition by a known method immediately before using the adhesive composition. Further, the polymerization initiator may be diluted with the organic solvent described in the above (additional solvent) column and then blended in the adhesive composition. Further, also in the adhesive composition according to the present embodiment, a thermal polymerization inhibitor may be added to the additive solvent.

<Adhesive film>
In the adhesive film according to the embodiment of the present invention (Embodiment 3), an adhesive layer made of the adhesive composition according to the embodiment of the present invention is formed on the film. By using such an adhesive film, an adhesive layer can be suitably formed on the support. Therefore, an adhesive film formed by using the adhesive composition according to one embodiment is also within the scope of the present invention.

As a method for forming the adhesive layer on the film, a known method is appropriately used according to the desired film thickness and uniformity of the adhesive layer, and the dry film thickness of the adhesive layer is 10 to 1 on the film. A method of applying the adhesive composition so as to have a thickness of 000 μm can be mentioned.

When such an adhesive film is used, an adhesive layer having good film thickness uniformity and surface smoothness is formed as compared with the case where the adhesive composition is directly applied onto the support to form the adhesive layer. can do.

The film used for manufacturing the adhesive film is a release film that can peel off the adhesive layer formed on the film from the film and transfer the adhesive layer onto a surface to be treated such as a support. Well, it is not particularly limited. For example, a flexible film made of a synthetic resin film such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, and polyvinyl chloride having a film thickness of 15 to 125 μm can be mentioned. If necessary, the film is preferably subjected to a mold release treatment so as to facilitate transfer.

Further, the adhesive film may be protected by covering the exposed surface of the adhesive layer with a protective film. The protective film is not limited as long as it can be peeled off from the adhesive layer, but for example, polyethylene terephthalate film, polypropylene film, and polyethylene film are preferable. Further, each protective film is preferably coated with silicone or baked in order to facilitate peeling from the adhesive layer.

The method of using the adhesive film is not particularly limited, but for example, when a protective film is used, it is peeled off and an exposed adhesive layer is layered on the support to be applied on the film (adhesive). A method of thermocompression bonding the adhesive layer to the surface of the support by moving the heating roller from the back surface of the surface on which the agent layer is formed can be mentioned.

The protective film peeled off from the adhesive film can be stored and reused by sequentially winding it into a roll with a roller such as a winding roller.

[Laminate]
In the laminated body, an adhesive layer having high heat resistance, high chemical resistance, and high detergency is formed by applying the adhesive composition according to one embodiment on a support. In the laminated body, a sealing substrate having a sealing body in which an element is sealed by a sealing material and a rewiring layer on one flat surface portion of the sealing body is formed on an adhesive layer. That is, the laminate is a laminate produced in the process of manufacturing a sealing substrate based on a fan-out type technology in which terminals provided on the element are mounted on a rewiring layer extending outside the chip area.

[Encapsulating substrate]
The sealing substrate (board) includes an element, a rewiring layer on which the element is mounted, and a sealing body that seals the element. The sealing substrate preferably includes a plurality of elements, and a plurality of electronic components can be obtained by dicing such a sealing substrate.

(Rewiring layer)
The rewiring layer is also called an RDL (Redistribution Layer), and is a thin-film wiring body constituting a wiring connected to an element, and may have a single-layer or a plurality of-layer structure. In one embodiment, the rewiring layer is made of a dielectric (eg, silicon oxide (SiO _x ), a photosensitive resin such as photosensitive epoxy) and a conductor (eg, aluminum, copper, titanium, nickel, gold and silver). The wiring may be formed of a metal such as silver-tin alloy or an alloy such as silver-tin alloy), but is not limited thereto.

(element)
The element (bare chip) is a semiconductor element or other element, and may have a single-layer or multi-layer structure. When the element is a semiconductor element, the electronic component obtained by dicing the sealing substrate is a semiconductor device.

(Encapsulant)
As the sealing material, for example, a sealing material containing an epoxy-based resin and a silicone-based resin can be used. The sealing material is not provided for each element, but preferably one that integrally seals all of the plurality of elements mounted on the rewiring layer.

[Support]
The support may have the strength necessary to prevent damage or deformation of each component of the sealing substrate when the sealing substrate is formed. Further, the support is formed of a material that transmits light having a wavelength capable of altering the separation layer formed on the support.

As the material of the support, for example, glass, silicon, acrylic resin and the like can be used, but the material is not limited thereto. As the shape of the support, for example, a support such as a rectangle or a circle can be used, but the shape is not limited thereto.

[Adhesive layer]
The adhesive layer is formed by the adhesive composition according to the embodiment of the present invention, and is a layer for fixing the sealing substrate on the support. An element for sealing with a sealing material may be arranged on the surface of the adhesive layer. Further, the adhesive layer may form a pattern such as a photosensitive insulating film by directly applying, for example, a photoresist or the like to the surface thereof and exposing the adhesive layer. Further, the adhesive layer also has a function of protecting the separation layer.

The thickness of the adhesive layer may be appropriately set according to the type of the support and the sealing substrate, the treatment to be performed when forming the sealing substrate, and the like, but it may be 0.1 μm or more and 50 μm or less. It is preferably 1 μm or more and 10 μm or less, more preferably. When it is 1 μm or more, the sealing substrate can be suitably fixed on the support. When it is 10 μm or less, the removal of the adhesive layer can be facilitated in a later step.

[Separation layer]
The separation layer is a layer that is altered by irradiation with light. The support can be separated from the sealing substrate by irradiating the separation layer with light through the support to change the quality of the separation layer.

In addition, in this specification, "alteration" of a separation layer means a phenomenon in which the separation layer can be destroyed by receiving a slight external force or a state in which the adhesive force between the separation layer and the layer in contact with the separation layer is reduced. To do. As a result of the alteration of the separation layer caused by the absorption of light, the separation layer loses its strength or adhesiveness before being irradiated with light. That is, the separation layer becomes brittle by absorbing light. The alteration of the separation layer may mean that the separation layer undergoes decomposition due to the energy of absorbed light, a change in the molecular configuration, a dissociation of functional groups, or the like. Alteration of the separation layer occurs as a result of absorbing light.

Therefore, for example, the support plate and the substrate can be easily separated by changing the quality so that the separation layer is destroyed only by lifting the support plate. More specifically, for example, one of the substrate and the support plate in the laminated body is fixed to the mounting table by a support separating device or the like, and the other is held and lifted by a suction pad (suction portion) provided with a suction means or the like. By doing so, a force is applied by separating the support plate and the substrate, or by gripping the chamfered portion of the peripheral end portion of the support plate with a separation plate provided with a clamp (claw portion) or the like, and applying force to the substrate and the support plate. And should be separated. Further, for example, the support plate may be peeled from the substrate in the laminated body by a support separating device provided with a peeling means for supplying a peeling liquid for peeling the adhesive. By supplying the peeling liquid to at least a part of the peripheral end portion of the adhesive layer in the laminated body by the peeling means and swelling the adhesive layer in the laminated body, the force is concentrated on the separation layer from the swelled portion of the adhesive layer. In this way, force can be applied to the substrate and the support plate. Therefore, the substrate and the support plate can be suitably separated.

The force applied to the laminated body may be appropriately adjusted depending on the size of the laminated body and the like, and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, a force of about 0.1 to 5 kgf is applied. By adding, the substrate and the support plate can be suitably separated.

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

In addition, another layer may be further formed between the separation layer and the support. In this case, the other layer may be composed of a material that transmits light. Thereby, a layer having preferable properties and the like can be appropriately added without hindering the incident of light on the separation layer. The wavelengths of light that can be used differ depending on the type of material that constitutes the separation layer. Therefore, the material constituting the other layer does not need to transmit all the light, and can be appropriately selected from the materials capable of transmitting light having a wavelength capable of altering the material constituting the separation layer.

Further, the separation layer is preferably formed only from a material having a structure that absorbs light, but a material that does not have a structure that absorbs light is used as long as the essential properties in the present invention are not impaired. It may be added to form a separation layer. Further, it is preferable that the surface of the separation layer on the side facing the adhesive layer is flat (no unevenness is formed), whereby the separation layer can be easily formed and the separation layer can be evenly attached. It becomes possible.

(Fluorocarbon)
The separation layer may be made of fluorocarbon. Since the separation layer is composed of fluorocarbon, it is deteriorated by absorbing light, and as a result, the strength or adhesiveness before being irradiated with light is lost. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support and the sealing substrate can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed by a plasma CVD (chemical vapor deposition) method.

Fluorocarbons absorb light with wavelengths in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the fluorocarbon used for the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or more.

The light irradiated to the separation layer, in accordance with the fluorocarbon wavelength absorbable, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, a solid laser such as a fiber laser, a liquid laser dye laser, , CO ₂ laser, excimer laser, Ar laser, gas laser such as He-Ne laser, laser light such as semiconductor laser, free electron laser, or non-laser light may be appropriately used. The wavelength at which the fluorocarbon can be altered is not limited to this, and for example, a wavelength in the range of 600 nm or less can be used.

(Polymer containing a light-absorbing structure in its repeating unit)
The separation layer may contain a polymer containing a structure having light absorption in its repeating unit. The polymer is altered by being irradiated with light. The alteration of the polymer occurs when the structure absorbs the irradiated light. The separation layer loses its strength or adhesiveness before being irradiated with light as a result of alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support and the sealing substrate can be easily separated.

The above-mentioned structure having light absorption is a chemical structure that absorbs light and alters a polymer containing the structure as a repeating unit. The structure is, for example, an atomic group containing a conjugated π-electron system composed of a substituted or unsubstituted benzene ring, a fused ring or a heterocycle. More specifically, the structure may be a cardo structure or a benzophenone structure, a diphenylsulfoxide structure, a diphenylsulfone structure (bisphenylsulfone structure), a diphenyl structure or a diphenylamine structure existing in the side chain of the polymer.

When the structure is present in the side chain of the polymer, the structure can be represented by the following formula.

（式中、Ｒはそれぞれ独立して、アルキル基、アリール基、ハロゲン、水酸基、ケトン基、スルホキシド基、スルホン基又はＮ（Ｒ^４）（Ｒ^５）であり（ここで、Ｒ^４及びＲ^５はそれぞれ独立して、水素原子又は炭素数１〜５のアルキル基である）、Ｚは、存在しないか、又は−ＣＯ−、−ＳＯ_２−、−ＳＯ−若しくは−ＮＨ−であり、ｎは０又は１〜５の整数である。）
また、上記重合体は、例えば、以下の式のうち、（ａ）〜（ｄ）の何れかによって表される繰り返し単位を含んでいるか、（ｅ）によって表されるか、又は（ｆ）の構造をその主鎖に含んでいる。

(In the formula, R is independently an alkyl group, an aryl group, a halogen, a hydroxyl group, a ketone group, a sulfoxide group, a sulfone group or N (R ⁴ ) (R ⁵ ) (here, R ⁴ and R ^5). Are independently hydrogen atoms or alkyl groups with 1 to 5 carbon atoms), Z is absent or is -CO-, -SO _2- , -SO- or -NH-, and n is It is an integer of 0 or 1-5.)
Further, the polymer contains, for example, a repeating unit represented by any of (a) to (d) in the following formula, represented by (e), or according to (f). The structure is contained in its main chain.

（式中、ｌは１以上の整数であり、ｍは０又は１〜２の整数であり、Ｘは、（ａ）〜（ｅ）において上記の“化１”に示した式の何れかであり、（ｆ）において上記の“化１”に示した式の何れかであるか、又は存在せず、Ｙ_１及びＹ_２はそれぞれ独立して、−ＣＯ−又はＳＯ_２−である。ｌは好ましくは１０以下の整数である。）
上記の“化１”に示されるベンゼン環、縮合環及び複素環の例としては、フェニル、置換フェニル、ベンジル、置換ベンジル、ナフタレン、置換ナフタレン、アントラセン、置換アントラセン、アントラキノン、置換アントラキノン、アクリジン、置換アクリジン、アゾベンゼン、置換アゾベンゼン、フルオリム、置換フルオリム、フルオリモン、置換フルオリモン、カルバゾール、置換カルバゾール、Ｎ−アルキルカルバゾール、ジベンゾフラン、置換ジベンゾフラン、フェナントレン、置換フェナントレン、ピレン及び置換ピレンが挙げられる。例示した置換基がさらに置換基を有している場合、その置換基は、例えば、アルキル、アリール、ハロゲン原子、アルコキシ、ニトロ、アルデヒド、シアノ、アミド、ジアルキルアミノ、スルホンアミド、イミド、カルボン酸、カルボン酸エステル、スルホン酸、スルホン酸エステル、アルキルアミノ及びアリールアミノから選択される。

(In the formula, l is an integer of 1 or more, m is an integer of 0 or 1 to 2, and X is any of the formulas shown in the above “Chemical formula 1” in (a) to (e). Yes, either of the formulas shown in "Chemical formula 1" above in (f), or not present, and Y ₁ and Y ₂ are independently -CO- or SO _2- l. Is preferably an integer of 10 or less.)
Examples of the benzene ring, fused ring and heterocyclic ring shown in "Chemical formula 1" above include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthracene, substituted anthracene, acrydin and substituted. Examples thereof include acrydin, azobenzene, substituted azobenzene, fluorim, substituted fluorim, fluorimon, substituted fluorimon, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene and substituted pyrene. When the exemplified substituent has additional substituents, the substituents are, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, carboxylic acid, It is selected from carboxylic acid ester, sulfonic acid, sulfonic acid ester, alkylamino and arylamino.

Among the substituents represented by "Formula 1" above, a fifth substituent having two phenyl groups, Z is the -SO 2 _- an example of a case where the bis (2, 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis Examples thereof include (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone.

Among the substituents shown in "Chemical formula 1" above, the fifth substituent having two phenyl groups, in which Z is -SO-, is an example of bis (2,3). -Dihydroxyphenyl) sulfoxide, bis (5-chloro-2,3-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxy-6-methylphenyl) sulfoxide, bis (5) -Chloro-2,4-dihydroxyphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (3,5-dihydroxyphenyl) sulfoxide, bis (2,3) , 4-Trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy-6-methylphenyl) -sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2, Examples thereof include 4,6-trihydroxyphenyl) sulfoxide and bis (5-chloro-2,4,6-trihydroxyphenyl) sulfoxide.

Of the substituents shown in "Chemical formula 1" above, the fifth substituent having two phenyl groups, in which Z is -C (= O)-, is 2 as an example. , 4-Dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2' -Dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'- Examples thereof include methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2', 4'-dihydroxybenzophenone, 4-dimethylamino-3', 4'-dihydroxybenzophenone and the like.

When the structure is present in the side chain of the polymer, the ratio of the repeating unit containing the structure to the polymer is such that the light transmittance of the separation layer is 0.001% or more and 10%. It is within the following range. If the polymer is prepared so that the ratio falls within such a range, the separation layer can sufficiently absorb light and can be reliably and rapidly denatured. That is, the support can be easily removed from the sealing substrate, and the light irradiation time required for the removal can be shortened.

The structure can absorb light having a wavelength in a desired range, depending on the type of selection. For example, the wavelength of light that can be absorbed by the structure is more preferably in the range of 100 nm or more and 2,000 nm or less. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, for example, in the range of 100 nm or more and 500 nm or less. For example, the structure can alter the polymer containing the structure by absorbing ultraviolet light having a wavelength in the range of preferably about 300 nm or more and 370 nm or less.

Lights that can be absorbed by the above structure include, for example, a high-pressure mercury lamp (wavelength: 254 nm or more and 436 nm or less), a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), and an F2 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: 405 nm) Wavelength: 365 nm) and the like.

The above-mentioned separation layer contains a polymer containing the above-mentioned structure as a repeating unit, but the separation layer may further contain a component other than the above-mentioned polymer. Examples of the component include a filler, a plasticizer, and a component capable of improving the peelability of the support. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote the absorption of light by the above structure and the alteration of the polymer.

(Inorganic substance)
The separation layer may be made of an inorganic substance. Since the separation layer is composed of an inorganic substance, it is deteriorated by absorbing light, and as a result, the strength or adhesiveness before being irradiated with light is lost. Therefore, by applying a slight external force (for example, lifting the support 1), the separation layer is broken, and the support and the sealing substrate can be easily separated.

The inorganic substance may have a structure that is altered by absorbing light, and for example, one or more kinds of inorganic substances selected from the group consisting of metals, metal compounds and carbon can be preferably used. The metal compound refers to a compound containing a metal atom, and may be, for example, a metal oxide or a metal nitride. Examples of such inorganic substances include, but are not limited to, gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more kinds of inorganic substances selected from the group of Note that carbon is a concept that may include allotropes of carbon, and may be, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.

The inorganic substance absorbs light having a wavelength in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the inorganic substance used for the separation layer, the above-mentioned inorganic substance can be suitably altered.

The light irradiated to the separation layer made of an inorganic substance, depending on the wavelength capable of absorbing the inorganic material, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, a solid laser such as a fiber laser, 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 lasers may be appropriately used.

The separation layer made of an inorganic substance can be formed on the support by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like. The thickness of the separation layer made of an inorganic substance is not particularly limited as long as it can sufficiently absorb the light to be used. For example, the film thickness may be within the range of 0.05 μm or more and 10 μm or less. More preferable. Further, an adhesive may be applied in advance to both sides or one side of an inorganic film (for example, a metal film) made of an inorganic substance constituting the separation layer, and the adhesive may be attached to the support.

When a metal film is used as the separation layer, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer, the type of laser light source, and the laser output. Therefore, it is preferable to provide antireflection films and antistatic films on the top and bottom or either of the separation layers to take measures against them.

(Compound with infrared absorbing structure)
The separation layer may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer loses its strength or adhesiveness before being irradiated with infrared rays as a result of alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support and the sealing substrate can be easily separated.

Examples of the compound having an infrared absorbing structure or a compound having an infrared absorbing structure include alkane, alkene (vinyl, trans, cis, vinylidene, tri-substituted, tetra-substituted, conjugated, cumlen, etc.). Cyclic), Alkin (mono-substituted, di-substituted), monocyclic aromatics (benzene, mono-substituted, di-substituted, tri-substituted), alcohols and phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated) Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxylan ring ether, peroxide ether, ketone, dialkylcarbonyl, Aromatic carbonyl, 1,3-diketone enol, o-hydroxyarylketone, dialkylaldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, Aromatic esters, lactones (β-, γ-, δ-), aliphatic acid compounds, aromatic acidified compounds, acid anhydrides (conjugated, unconjugated, cyclic, acyclic), primary amides, Secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, primary Secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, isocyanic acid ester, thiocyan acid ester, aliphatic isothiocyanate ester, aromatic isothiocyanic acid Estere, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosoamine, nitrate ester, nitrite ester, nitroso bond (aliphatic, aromatic, monomer, dimer), mercaptan and thiophenol, thiol acid, etc. Sulfur compound, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or It can be a halogen), a PA ² bond (A ² is an H, C or O), or a Ti-O bond.

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

As the structure including the above Si-A ¹ bond, 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 , SiF _{3 and the} like can be mentioned. As the structure containing the Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

The ^{structures containing the PA 2} bond include PH, PH ₂ , P-CH ₃ , P-CH _2- , P-C ₆ H ₅ , A ³ ₃ -PO (A ³ is an aliphatic or aromatic). (Group), (A ⁴ O) _3- P-O (A ⁴ is alkyl), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , P-O-P, P-OH, and O = P-OH and the like can be mentioned.

The structure can absorb infrared rays having a wavelength in a desired range, depending on the type of selection. Specifically, the wavelength of infrared rays that can be absorbed by the structure is, for example, in the range of 1 μm or more and 20 μm or less, and more preferably in the range of 2 μm or more and 15 μm or less. Further, when the structure is a Si—O bond, a Si—C bond and a Ti—O bond, it can be in the range of 9 μm or more and 11 μm or less. Those skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each structure. For example, as an absorption band in each structure, Non-Patent Documents: SILVERSTEIN, BASSLER, MORRRILL, "Identification method by spectrum of organic compounds (5th edition) -Combination of MS, IR, NMR, UV-" (published in 1992) The description on pages 146 to 151 can be referred to.

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

To give an example, examples of the compound having a siloxane skeleton include a resin which is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2), or a resin. A resin which is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit derived from an acrylic compound can be used.

（化学式（２）中、Ｒ^６は、水素、炭素数１０以下のアルキル基、又は炭素数１０以下のアルコキシ基である。）
中でも、シロキサン骨格を有する化合物としては、上記化学式（１）で表される繰り返し単位及び下記化学式（３）で表される繰り返し単位の共重合体であるｔ−ブチルスチレン（ＴＢＳＴ）−ジメチルシロキサン共重合体がより好ましく、上記化学式（２）で表される繰り返し単位及び下記化学式（３）で表される繰り返し単位を１：１で含む、ＴＢＳＴ−ジメチルシロキサン共重合体がさらに好ましい。

(In the chemical formula (2), R ⁶ is a hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms.)
Among them, the compound having a siloxane skeleton includes t-butylstyrene (TBST) -dimethylsiloxane, which is a copolymer of a repeating unit represented by the above chemical formula (1) and a repeating unit represented by the following chemical formula (3). A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above chemical formula (2) and a repeating unit represented by the following chemical formula (3) in a ratio of 1: 1 is further preferable.

また、シルセスキオキサン骨格を有する化合物としては、例えば、下記化学式（４）で表される繰り返し単位及び下記化学式（５）で表される繰り返し単位の共重合体である樹脂を用いることができる。

Further, as the compound having a silsesquioxane skeleton, for example, a resin which is a copolymer of a repeating unit represented by the following chemical formula (4) and a repeating unit represented by the following chemical formula (5) can be used. ..

（化学式（４）中、Ｒ^７は、水素又は炭素数１以上、１０以下のアルキル基であり、化学式（５）中、Ｒ^８は、炭素数１以上、１０以下のアルキル基、又はフェニル基である。）
シルセスキオキサン骨格を有する化合物としては、このほかにも、特開２００７−２５８６６３号公報（２００７年１０月４日公開）、特開２０１０−１２０９０１号公報（２０１０年６月３日公開）、特開２００９−２６３３１６号公報（２００９年１１月１２日公開）、及び特開２００９−２６３５９６号公報（２００９年１１月１２日公開）において開示されている各シルセスキオキサン樹脂を好適に利用することができる。

(In the chemical formula (4), R ⁷ is hydrogen or an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, and in the chemical formula (5), R ⁸ is an alkyl group having 1 or more carbon atoms or 10 or less carbon atoms or a phenyl group. Is.)
Other compounds having a silsesquioxane skeleton include JP-A-2007-258663 (published October 4, 2007) and JP-A-2010-120901 (published June 3, 2010). Preferable use of each silsesquioxane resin disclosed in JP-A-2009-263316 (published on November 12, 2009) and JP-A-2009-263596 (published on November 12, 2009). be able to.

Among them, as the compound having a silsesquioxane skeleton, a copolymer of a repeating unit represented by the following chemical formula (6) and a repeating unit represented by the following chemical formula (7) is more preferable, and the following chemical formula (6) is used. A copolymer containing a repeating unit represented by the following and a repeating unit represented by the following chemical formula (7) in a ratio of 7: 3 is more preferable.

シルセスキオキサン骨格を有する重合体としては、ランダム構造、ラダー構造、及び籠型構造があり得るが、何れの構造であってもよい。

The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a cage-shaped structure, but any structure may be used.

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. Ekoxytitanium such as (ii) di-i-propoxybis (acetylacetonato) titanium, and chelated titanium such as propanedioxytitanium bis (ethylacetacetate); (iii) i-C ₃ H ₇ O- [- Ti (O-i-C ₃ H ₇ ) _2- O-] _n- i-C ₃ H ₇ , and n-C ₄ H ₉ O- [-Ti (On-C ₄ H ₉ ) _2- O _-] n _-n-C 4 titanium polymers such as _{H 9;} (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- propoxytitanium diisostearate, and (2-n-butoxy Acrylate titanium such as carbonylbenzoyloxy) tributoxytitanium; and water-soluble titanium compounds such as (v) di-n-butoxybis (triethanolaminoto) titanium can be mentioned.

Among them, as a compound containing a Ti—O bond, di-n-butoxy-bis (triethanolamineto) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ]] ₂ ) is preferable.

The above-mentioned separation layer contains a compound having an infrared absorbing structure, but the separation layer may further contain a component other than the above-mentioned compound. Examples of the component include a filler, a plasticizer, and a component capable of improving the peelability of the support. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote the absorption of infrared rays by the above structure and the alteration of the compound.

(Infrared absorber)
The separation layer may contain an infrared absorbing substance. The separation layer is configured to contain an infrared absorbing substance so that it is altered by absorbing light, and as a result, the strength or adhesiveness before being irradiated with light is lost. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is broken, and the support and the sealing substrate can be easily separated.

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

(Reactive polysilsesquioxane)
The separation layer can be formed by polymerizing the reactive polysilsesquioxane. As a result, the separation layer has high chemical resistance and high heat resistance.

In the present specification, the reactive polysilsesquioxane is a silanol group at the end of the polysilsesquioxane skeleton, or a polysilseski having a functional group capable of forming a silanol group by hydrolysis. It is an oxane and can be polymerized with each other by condensing the silanol group or the functional group capable of forming the silanol group. Further, the reactive polysilsesquioxane has a silsesquioxane skeleton such as a random structure, a cage-shaped structure, or a ladder structure if it has a silanol group or a functional group capable of forming a silanol group. Reactive polysilsesquioxane can be employed.

Further, it is more preferable that the reactive polysilsesquioxane has a structure represented by the following chemical formula (8).

化学式（８）中、Ｒ”は、それぞれ独立して、水素及び炭素数１以上、１０以下のアルキル基からなる群より選択され、水素及び炭素数１以上、５以下のアルキル基からなる群より選択されることがより好ましい。Ｒ”が、水素又は炭素数１以上、１０以下のアルキル基であれば、分離層形成工程における加熱によって、化学式（８）によって表される反応性ポリシルセスキオキサンを好適に縮合させることができる。

In the chemical formula (8), R "is independently selected from the group consisting of hydrogen and alkyl groups having 1 or more and 10 or less carbon atoms, and from the group consisting of hydrogen and alkyl groups having 1 or more and 5 or less carbon atoms. More preferably, it is more preferably selected. If R "is hydrogen or an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, the reactive polysilsesquioki represented by the chemical formula (8) is generated by heating in the separation layer forming step. Sun can be suitably condensed.

In the chemical formula (8), p is preferably an integer of 1 or more and 100 or less, and more preferably an integer of 1 or more and 50 or less. By providing the repeating unit represented by the chemical formula (8), the reactive polysilsesquioxane has a higher content of Si—O bond than that formed by using other materials, and has an infrared ray (0.78 μm or more). , 1,000 μm or less), preferably far infrared rays (3 μm or more, 1,000 μm or less), and more preferably a separation layer having high absorbance at a wavelength of 9 μm or more and 11 μm or less can be formed.

Further, in the chemical formula (8), R'is an organic group that is the same as or different from each other independently. Here, R is, for example, an aryl group, an alkyl group, an alkenyl group, or the like, and these organic groups may have a substituent.

When R'is an aryl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like can be mentioned, and a phenyl group is more preferable. Further, the aryl group may be bonded to the polysilsesquioxane skeleton via an alkylene group having 1 to 5 carbon atoms.

When R'is an alkyl group, examples of the alkyl group include linear, branched or cyclic alkyl groups. When R is an alkyl group, the number of carbon atoms is preferably 1 to 15, and more preferably 1 to 6. When R is a cyclic alkyl group, it may be an alkyl group having a monocyclic or 2 to 4 cyclic structure.

When R'is an alkenyl group, as in the case of an alkyl group, a linear, branched or cyclic alkenyl group can be mentioned, and the alkenyl group may have 2 to 15 carbon atoms. It is preferably 2 to 6, and more preferably 2 to 6. When R is a cyclic alkenyl group, it may be an alkenyl group having a monocyclic or 2-4 cyclic structure. Examples of the alkenyl group include a vinyl group and an allyl group.

Further, examples of the substituent that R'can have include a hydroxyl group and an alkoxy group. When the substituent is an alkoxy group, a linear, branched, or cyclic alkylalkoxy group can be mentioned, and the number of carbon atoms in the alkoxy group is preferably 1 to 15, preferably 1 to 10. Is more preferable.

From one viewpoint, the siloxane content of the reactive polysilsesquioxane is preferably 70 mol% or more and 99 mol% or less, and more preferably 80 mol% or more and 99 mol% or less. .. When the siloxane content of the reactive polysilsesquioxane is 70 mol% or more and 99 mol% or less, it is preferable to irradiate with infrared rays (preferably far infrared rays, more preferably light having a wavelength of 9 μm or more and 11 μm or less). It is possible to form a separation layer that can be altered to.

Further, from one viewpoint, the weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 or more and 50,000 or less, and more preferably 1,000 or more and 10,000 or less. preferable. When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is 500 or more and 50,000 or less, it can be suitably dissolved in a solvent and can be suitably applied on a support plate.

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

<Manufacturing method of laminated body and substrate processing method>
A method for manufacturing a laminated body according to an embodiment of the present invention (Embodiment 4) includes a rewiring layer on which an element is mounted and a sealing body in which the element is sealed with a sealing material. A method for producing a laminated body in which a substrate is laminated on a support supporting the sealing substrate via an adhesive layer, and the above-mentioned adhesive composition is applied onto the support. It includes an adhesive layer forming step of forming an adhesive layer. Further, in the method for producing a laminated body according to the present embodiment, the support is a support made of a material that transmits light, and is altered by irradiating the support with light before the adhesive layer forming step. It includes a separation layer forming step of forming a separation layer to be formed.

Further, in the substrate processing method according to the present embodiment, the laminate is manufactured by the method for producing the laminate according to the embodiment of the present invention, and then light is irradiated through the support to separate the laminate. It includes a separation step of separating the support from the laminate by altering the layer, and a removal step of removing the residue of the adhesive layer remaining on the sealing substrate side with a cleaning liquid after the separation step. ..

FIG. 1 is a diagram illustrating each step in the method for manufacturing a laminate and the method for processing a substrate according to the first embodiment of the present invention. In the method for producing a laminate according to the present embodiment, the separation layer forming step, the adhesive layer forming step, and the sealing substrate forming step are carried out in this order.

[Separation layer forming step]
As shown in FIG. 1A, in the separation layer forming step, one flat surface portion 1a of the support 1 that transmits light is irradiated with light by, for example, a chemical vapor deposition (CVD) method. The separation layer 2 that is denatured by is formed. The "one flat surface portion" refers to one of the flat surface portions of the support 1. Further, the "flat surface portion" may have fine irregularities that can be regarded as a substantially flat surface.

[Adhesive layer forming process]
As shown in FIG. 1B, in the adhesive layer forming step, for example, the above-mentioned adhesive composition is applied and heated by a method such as spin coating, dipping, roller blade, spray coating, slit coating or the like. Alternatively, the diluting solvent contained in the adhesive composition is removed by placing it in a reduced pressure environment. After that, when the adhesive layer contains a thermal polymerization initiator, it is preferable to polymerize the curable monomer contained in the adhesive layer by heating. The conditions for heating the adhesive layer 3 may be appropriately set based on the 1-minute half-temperature and the 1-hour half-temperature of the thermal polymerization initiator, and are, for example, within the range of 50 ° C. or higher and 300 ° C. or lower. At temperature, it is preferable to carry out under vacuum or in an atmosphere of an inert gas such as nitrogen gas, and more preferably to carry out under an atmosphere of an inert gas such as nitrogen gas.

When the adhesive layer contains a photopolymerization initiator, it is preferable to polymerize the curable monomer contained in the adhesive layer by exposing it in an atmosphere of an inert gas such as nitrogen gas. The exposure conditions may be appropriately set according to the type of photopolymerization initiator and the like.

If the adhesive layer 3 does not contain a curable monomer, it is not always necessary to heat or expose the adhesive layer 3 after removing the solvent.

[Encapsulation substrate forming process]
As shown in FIGS. 1 (c) to 1 (f), in the sealing substrate forming step, the sealing substrate 7 is formed on the adhesive layer 3. In the sealing substrate forming step in the present embodiment, the rewiring layer forming step, the mounting step, the sealing step, and the thinning step are performed in this order.

[Rewiring layer forming process]
As shown in FIG. 1 (c), in the rewiring layer forming step, the rewiring layer 4 is formed on the adhesive layer 3.

In one embodiment, as a procedure for forming the rewiring layer 4, first, _{a dielectric layer such as silicon oxide (SiO x} ) or a photosensitive resin is formed on the adhesive layer 3. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin by, for example, spin coating, dipping, roller blades, spray coating, slit coating, or the like.

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

In this way, when performing photolithography treatment, etching treatment, etc., the adhesive layer 3 dissolves an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), and a resist agent. Is exposed to the resist solvent of. As the resist solvent, PGMEA, cyclopentanone, N-methyl-2-pyrrolidone (NMP), cyclohexanone and the like are used. However, the adhesive layer 3 has enhanced chemical resistance by polymerizing a curable monomer in the cycloolefin polymer. Therefore, it is possible to prevent the adhesive layer 3 from being dissolved or peeled off by being exposed to not only acids and alkalis but also these resist solvents. Therefore, a highly accurate pattern can be formed on the adhesive layer 3 with a resist agent, and the rewiring layer 4 can be suitably formed.

Further, in the rewiring layer forming step, for example, in order to cure the resist agent formed on the adhesive layer 3, a heat treatment is performed for about 4 hours in a high temperature environment of 200 ° C. At this time, since the adhesive layer 3 has high heat resistance, it is possible to prevent cracks from occurring in the adhesive layer. Further, since the adhesive layer 3 has high heat resistance, it preferably prevents the resist film formed on the adhesive layer 3 from shrinking (shrinking) when exposed to a high temperature environment for a long time. be able to. Therefore, the rewiring layer 4 can be suitably formed on the adhesive layer 3.

As shown in FIG. 1D, in the mounting step, the element 5 is mounted on the rewiring layer 4. The element 5 can be mounted on the rewiring layer 4 by using, for example, a chip mounter or the like. If the element 5 is mounted on the rewiring layer 4 via the solder bumps in the mounting step, the solder bumps may be sealed by underfilling before the element 5 is sealed. ..

As shown in FIG. 1 (e), in the sealing step, the element 5 is sealed with the sealing material 6. The sealing material 6 is not particularly limited, and is compression-molded using a molding die while maintaining a high viscosity state, for example, in a state of being heated to 130 ° C. to 170 ° C. Therefore, when the element 5 is sealed by the sealing material 6, the adhesive layer 3 is pressurized at a temperature of 130 ° C. to 170 ° C. with the element 5 arranged. However, since the adhesive layer 3 has high heat resistance, it is preferable to prevent the rewiring layer 4 on which the element 5 is arranged from being distorted by being pressurized at a temperature of 130 ° C. to 170 ° C. Can be done.

As shown in FIG. 1 (f), the sealing material 6 is thinned in the thinning step. The sealing material 6 may be thinned to the same thickness as the element 5, for example.

Further, after the thinning step, treatments such as forming bumps on the sealing material and forming an insulating layer may be further performed.

The laminate 8 shown in FIG. 1 (g) obtained by the above steps includes a support 1 that transmits light, a separation layer 2 that is altered by irradiation with light, an adhesive layer 3, and a sealing substrate. 7 and 7 are laminated in this order, and the sealing substrate 7 is provided on one flat surface portion of the sealing body sealed by the sealing material 6 for sealing the element 5 and the sealing material. It includes a rewiring layer 4 on which the element 5 is arranged.

[Separation process]
As shown in FIG. 1 (h), in the separation step, the separation layer 2 is altered by irradiating the separation layer 2 with light L via the support 1. The type and wavelength of the light L to be irradiated may be appropriately selected according to the transparency of the support 1 and the material of the separation layer 2. For example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and a fiber. Use solid lasers such as lasers, liquid lasers such as dye lasers _{, gas lasers such as CO 2} lasers, excima lasers, Ar lasers, and He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, or non-laser light. be able to. As a result, the separation layer 2 can be altered so that the support 1 and the sealing substrate 7 can be easily separated.

Further, examples of the laser light irradiation conditions for irradiating the laser light include, but are not limited to, the following conditions: the average output value of the laser light is 1.0 W or more and 5.0 W or less. It is 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. Preferred; the scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less.

After that, as shown in FIG. 1 (i), the support 1 and the sealing substrate 7 are separated in the separation step. For example, the support 1 and the sealing substrate 7 are separated by applying a force in a direction in which the support 1 and the sealing substrate 7 are separated from each other. For example, while one of the support 1 and the sealing substrate 7 is fixed to the stage, the support 1 and the sealing substrate 7 are lifted while being sucked and held by a separation plate provided with a suction pad such as a bellows pad. And can be separated.

[Removal process]
As shown in FIG. 1 (h), in the removing step, the adhesive layer 3 and the separating layer 2 remaining on the sealing substrate 7 from which the support 1 is separated are removed. For example, a removal step of removing the residue of the adhesive layer 3 and the separation layer 2 with a cleaning liquid or the like containing an organic solvent is performed. For the adhesive layer 3, a diluting solvent used in the adhesive composition, that is, a hydrocarbon solvent can be preferably used as the cleaning liquid, and in particular, a terpene solvent such as p-menthane and a condensed ring carbide such as tetrahydronaphthalene can be used. It is more preferable to use hydrogen.

From the above, the isolated sealing substrate 7 can be obtained.

Further, the sealing substrate 7 may be subjected to treatments such as solder ball formation, dicing treatment, and oxide film formation.

[Embodiment 5]
Another embodiment of the present invention (Embodiment 5) will be described below. For convenience of explanation, the same reference numerals will be added to the members having the same functions as the members described in the above embodiment, and the description thereof will be omitted. In the method for manufacturing the laminate and the method for treating the substrate according to the second embodiment, the separation layer forming step, the adhesive layer forming step, the sealing substrate forming step, the separating step, and the removing step are carried out in this order, and the sealing substrate forming step is carried out. Then, the element is arranged on the adhesive layer 3. As shown in FIG. 2A, the separation layer forming step is the same as that of the first embodiment, and thus the description thereof will be omitted.

[Adhesive layer forming process]
In the adhesive layer forming step included in the method for producing a laminate according to the present embodiment, the adhesive composition according to one embodiment is applied onto the support 1 and adhered under the same conditions as in the first embodiment. The diluting solvent contained in the agent composition is removed, but the adhesive layer is not cured by further heating or exposure.

[Encapsulation substrate forming process]
As shown in FIGS. 2C to 2F, in the sealing substrate forming step, the sealing substrate 7 is formed on the adhesive layer 3. In the sealing substrate forming step in the present embodiment, the arrangement step, the sealing step, the thinning step, and the rewiring layer forming step are performed in this order.

As shown in FIG. 2C, in the arrangement step, the element 5 is arranged on the adhesive layer 3. More specifically, in the arrangement step, the support 1 on which the adhesive layer 3 is formed is heated to about 100 ° C., and the element 5 is crimped to the adhesive layer 3 by, for example, a die bonder or the like. 5 is placed on the adhesive layer 3.

When the adhesive layer contains a thermal polymerization initiator, the curability contained in the adhesive layer 3 is obtained by heating the adhesive layer 3 after arranging the element 5 on the adhesive layer 3 in the arrangement step. It is advisable to polymerize the monomer. When the adhesive layer contains a photopolymerization initiator, it is preferable to cure the adhesive layer 3 by exposing it.

As shown in FIG. 2D, in the sealing step, the element 5 is sealed with the sealing material 6. In the sealing step, as in the case of the first embodiment, when the element 5 is sealed with the sealing material 6, the adhesive layer 3 is pressurized at a temperature of 130 ° C. to 170 ° C. with the element 5 arranged. Will be done. However, since the adhesive layer 3 has high heat resistance, the position of the element 5 on the adhesive layer 3 caused by being pressurized by the sealing material 6 under the temperature condition of 130 ° C. to 170 ° C. It is possible to prevent the deviation. Therefore, the sealing substrate 7 in which the elements 5 are arranged with high accuracy can be suitably formed on the adhesive layer 3.

As shown in FIG. 2 (e), the sealing material 6 is thinned in the thinning step. The encapsulant 6 may be thinned, for example, until the terminal portion of the element 5 is exposed from the encapsulant 6.

As shown in FIG. 2 (f), in the rewiring layer forming step, the rewiring layer 4 is formed on the flat surface portion where the element 5 of the sealing body is exposed.

In the present embodiment, the procedure for forming the rewiring layer 4 can be performed in the same manner as in the first embodiment, and thus the description thereof will be omitted.

By the above steps, the laminated body 9 can be obtained as in the first embodiment.

Then, as shown in FIGS. 2 (g) and 2 (h), in the separation step, the support 1 is changed by irradiating the separation layer 2 with light to change the quality of the separation layer 2. Separate from the laminate 9. Further, after that, in the removing step, the sealing substrate 7 can be obtained by removing the adhesive layer 3 with a hydrocarbon solvent as in the first embodiment ((i) of FIG. 2).

[Embodiment 6]
The sixth embodiment of the present invention will be described as follows. For convenience of explanation, the same reference numerals will be added to the members having the same functions as the members described in the above-described first and second embodiments, and the description thereof will be omitted. The method for manufacturing the laminate and the method for manufacturing the sealing substrate according to the third embodiment include a separation layer forming step, a separating layer peripheral edge removing step, an adhesive layer forming step, a sealing substrate forming step, and an adhesive layer removing step. Perform in order.

[Separation layer forming step]
As shown in FIG. 3A, the separation layer forming step is the same as in the first and second embodiments, and thus the description thereof will be omitted.

[Separation layer peripheral edge removal step]
As shown in FIG. 3B, in the separation layer peripheral edge portion removing step, for example, the separation layer 2 formed on the entire circumference of the peripheral edge portion 1b of the support 1 is removed by EBR (Edge Bead Removal) treatment. The peripheral edge portion 1b is a peripheral edge portion of the flat surface portion 1a. As a result, as shown in FIG. 3B, the separation layer 2 is formed on the flat surface portion 1a in the portion surrounded by the peripheral edge portion 1b from which the separation layer 2 has been removed. The details of the EBR processing will be described later.

[Adhesive layer forming process]
As shown in FIG. 3C, in the adhesive layer forming step, the adhesive layer 3 is formed on the surface of the support 1 on the side where the separation layer 2 is removed from the entire circumference of the peripheral edge portion 1b. As a result, the entire surface of the separation layer 2 formed on the support 1 is covered with the adhesive layer 3. Since the method of forming the adhesive layer 3 is the same as that of the first embodiment, the description thereof will be omitted.

[Encapsulation substrate forming process]
As shown in FIGS. 3D to 3G, in the sealing substrate forming step, the sealing substrate 7'is formed on the adhesive layer 3. In the sealing substrate forming step in the present embodiment, the rewiring layer forming step, the mounting step, the sealing step, and the thinning step are performed in this order.

As shown in FIG. 3D, in the third embodiment, in the rewiring layer forming step, the outer peripheral end portion of the rewiring layer 4 formed on the adhesive layer 3 is removed by a trimming process. The rewiring layer 4 may be trimmed by grinding with a known means such as a grinder. Thereby, in the subsequent step, the EBR treatment can be suitably performed on the laminated body 8'(FIG. 3).

Since the method of forming the rewiring layer 4 is the same as that of the first embodiment, the description thereof will be omitted.

As shown in FIGS. 3 (e) to 3 (g), the mounting step, the sealing step, and the thinning step are also performed in the third embodiment. Since the mounting step, the sealing step, and the thinning step in the third embodiment can be performed in the same manner as in the first embodiment, the description thereof will be omitted.

[Adhesive layer removal process]
As shown in FIG. 3H, in the adhesive layer removing step, for example, the adhesive layer 3 formed on the entire circumference of the peripheral edge portion 1b of the support 1 is removed by EBR treatment. Of the adhesive layer 3, the portion formed on the entire circumference of the peripheral edge portion 1b of the support 1 does not go through the separation layer 2, but the support 1 and the sealing substrate 7'are bonded to each other. By removing it, the support 1 and the sealing substrate 7'can be smoothly separated when the separation layer 2 is altered.

In particular, by removing the adhesive layer 3 formed on the outer peripheral end portion 2a of the separation layer 2 formed on the support 1, the support 1 and the sealing substrate 7'are sure to be separated from each other. Since it can be in a state of being bonded via the separation layer 2, the support 1 and the sealing substrate 7'can be separated more smoothly when the separation layer 2 is altered.

[Separation process-removal process]
As shown in FIGS. 3 (i) to 3 (k), the sealed substrate 7'can be manufactured by performing the separation step and the removal step in the same manner as in the first embodiment.

(EBR processing)
In the above-mentioned (A) separation layer peripheral edge removal step, the EBR treatment for removing the separation layer 2 formed on the entire circumference of the peripheral edge 1b of the support 1, and in the (B) adhesive layer removal step, the support The EBR treatment for removing the adhesive layer 3 formed on the entire circumference of the peripheral portion 1b of 1 is, for example, physically using (i) a method of dissolving and removing with a solvent, (ii) a cutter or a blade, or the like. Examples thereof include a method of cutting and removing, and (iii) a method of removing by ashing under atmospheric pressure. Among these, a method of removing with a solvent is preferable from the viewpoint of strength and practicality.

The solvent used in the method of removing with a solvent may be any one that can dissolve the separation layer 2 or the adhesive layer 3 to be removed, and is not particularly limited. It can be selected as appropriate. For example, for the adhesive layer 3, a terpene-based solvent such as p-menthane, a condensed ring hydrocarbon such as tetrahydronaphthalene, or the like can be used. Further, with respect to the separation layer 2, for example, a primary aliphatic amine such as monoisopropanolamine (MIPA), a secondary aliphatic amine such as 2- (methylamino) ethanol, and a third such as triethanolamine. At least one amine selected from the group consisting of alicyclic amines such as class aliphatic amines, cyclohexylamines, aromatic amines such as benzylamine, and heterocyclic amines such as N-hydroxyethylpiperidin, or A solvent containing them can be used. As the solvent, an organic solvent other than the terpene solvent among those listed in the above (additional solvent) column can be preferably used.

Examples of the method of supplying the solvent include a method of supplying the solvent to the removal target by ejecting the solvent and a method of immersing the removal target in the solvent.

As a method of supplying the solvent to the removal target by ejecting the solvent, a method of supplying the solvent to the removal target while rotating the support 1 is preferable in order to supply the solvent uniformly. As a method of supplying the solvent while rotating the support 1, for example, a nozzle for ejecting the solvent is arranged directly above the peripheral portion 1b of the support 1, and the solvent is placed on the peripheral portion 1b of the support 1. A method of rotating the support 1 using a spinner while dropping the support 1 immediately to the outside can be mentioned. As a result, the solvent can be supplied to the immediate outside of the entire circumference of the peripheral edge portion 1b of the support 1. The number of nozzles to be arranged is not limited, and may be one or more.

In the above method involving the rotation of the support 1 and the ejection of the solvent, the rotation speed of the support 1, the flow rate of the solvent when the solvent is supplied from the nozzle, and the supply time of the solvent are determined by the composition of the removal target and the thickness of the removal target. Although it may differ depending on the type of solvent used and the degree of removal, a person skilled in the art can examine and determine the optimum conditions without difficulty.

Further, after the object to be removed by the solvent is dissolved, it is preferable to dry the support 1 and the like. By going through the drying step, it is possible to remove unnecessary solvents and solvents that have penetrated into the separation layer 2 or the adhesive layer 3 that is not the part to be removed.

Examples of the drying method include shake-off drying by rotating the support 1 using a spinner or the like, drying by air blowing by spraying nitrogen gas or the like, drying by baking, drying by decompression, and the like. As these drying methods, either a method using either method alone or a method using any two or more methods in combination is possible.

[Embodiment 7]
The seventh embodiment of the present invention will be described as follows. For convenience of explanation, the same reference numerals will be added to the members having the same functions as the members described in the above-described first to third embodiments, and the description thereof will be omitted. The method for manufacturing the laminate and the method for manufacturing the sealing substrate according to the fourth embodiment includes a separation layer forming step, a separating layer peripheral edge removing step, an adhesive layer forming step, a sealing substrate forming step, and an adhesive layer removing step. Perform in order.

[Separation layer forming process-adhesive layer forming process]
Since the separation layer forming step, the separation layer peripheral portion removing step, and the adhesive layer forming step are the same as those in the second embodiment, the description thereof will be omitted.

[Encapsulation substrate forming process]
In the sealing substrate forming step, the element 5 is arranged on the adhesive layer 3 and sealed. That is, the sealing substrate 7'is formed by the same process as in the second embodiment. Then, as shown in FIG. 4A, the outer peripheral end portion of the sealing substrate 7'is removed by a trimming process. The sealing substrate 7 may be trimmed by grinding with a known means such as a grinder. As a result, in a later step, the amine treatment can be suitably performed on the laminate 9'(FIG. 4).

[Adhesive layer removal process]
As shown in FIG. 4B, similarly to the third embodiment, in the fourth embodiment, the outer peripheral end portion of the sealing substrate 7'is trimmed to be outside the outer peripheral end portion 2a of the separation layer 2. The adhesive layer 3 formed on the surface can be removed. Therefore, when the separation layer 2 is altered, the support 1 and the sealing substrate 7'can be separated more smoothly.

After that, the sealing substrate 7'can be manufactured by removing the adhesive layer 3 with a hydrocarbon solvent in the same manner as in the first to third embodiments.

[Another Embodiment]
The method for producing a laminate and the method for treating a substrate according to the present invention are not limited to the above-described embodiments (4th embodiment, 5th embodiment, 6th embodiment, 7th embodiment). For example, in the method for manufacturing a laminate according to another embodiment, the sealing substrate in the laminate formed by the method for producing a laminate according to each embodiment is separated via another adhesive layer and another separation layer. This is a method for manufacturing a laminated body to be laminated on the support of the above. As a result, the support on the adhesive layer side used for forming the sealing substrate can be separated, and the sealing substrate can be suitably processed while the sealing substrate is supported by another support. it can.

Further, the method for manufacturing a laminate according to still another embodiment is a method for producing a laminate in which a substrate, an adhesive layer, and a support are laminated in this order, and is a method for producing a laminate on the substrate or on the substrate. Includes an adhesive layer forming step of applying the adhesive composition according to one embodiment of the present application to at least one of the supports and heating the adhesive layer to form the adhesive layer. Here, examples of the substrate include flexible substrates such as silicon, ceramics, and polyimide resins, which can typically be a silicon interposer.

According to the above configuration, for example, a silicon interposer can be suitably processed on the support to form a through electrode. That is, by forming the adhesive layer using the adhesive composition according to one embodiment, the laminate can be suitably formed even in the fan-in type semiconductor encapsulation technique.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

The adhesive compositions of Examples 1 to 15 were prepared using a base polymer and a curable monomer as resin components. At the same time, the adhesive compositions of Comparative Examples 1 to 4 are prepared, and then an adhesive layer is formed using the adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 4, and in each adhesive layer, The adaptability to the sealing of the element by the compression type and the adaptability to the insulation pattern forming process were evaluated.

[Preparation of adhesive composition and formation of adhesive layer]

(Example 1)
As the adhesive composition of Example 1, 85 parts by weight of APL6015 (cycloolefin polymer: manufactured by Mitsui Chemicals, Inc.) and 15 parts by weight of A-DCP (tricyclodecanedimethanol diacrylate: Shin-Nakamura) as a curable monomer. (Manufactured by Chemical Co., Ltd.) was dissolved in 400 parts by weight of decahydronaphthalene. Next, perloyl TCP (thermal polymerization initiator: manufactured by Nippon Oil & Fats Co., Ltd.) was added to 100 parts by weight of the curable monomer so as to have 2 parts by weight to prepare an adhesive composition. Parloyl TCP was dissolved in 10 parts by weight of butyl acetate (additional solvent) and added to the resin component.

Then, a glass support (10 cm × 10 cm, thickness 700 .mu.m) on the flow rate 400 sccm, pressure 700 mTorr, under the conditions of RF power 2500W and film-forming temperature 240 ° C., by a CVD method using _C 4 _{F 8} as a reactive gas , A fluorocarbon film (thickness 1 μm) which is a separation layer was formed.

Next, the adhesive composition of Example 1 was applied onto the separation layer formed on the glass support while rotating at 1500 rpm by a spin coating method. Subsequently, the glass support coated with the adhesive composition of Example 1 was preheated at 140 ° C. for 5 minutes to form an adhesive layer of Example 1 (thickness: 3 μm). The adhesive layer of Example 1 was used for the following evaluations 1 and 2, respectively.

(Examples 2 to 15)
As Examples 2 to 15, an adhesive composition was prepared by blending a base polymer, a curable monomer and a polymerization initiator in a composition and composition ratio different from those of Example 1. Subsequently, the adhesive layers of Examples 2 to 15 were formed using these adhesive compositions.

(Comparative Examples 1 to 4)
The adhesive compositions of Comparative Examples 1 to 4 were prepared according to the procedure for preparing the adhesive composition of Example 1, except that a cycloolefin polymer having a low glass transition temperature or a thermoplastic elastomer was used. Next, each of the adhesive compositions of Comparative Examples 1 to 4 was spin-coated on the glass support on which the separation layer was formed according to the same procedure as in Example 1, and preheated at 160 ° C. for 5 minutes. By doing so, an adhesive layer having a thickness of 5 μm was formed.

The base polymers and curable monomers used in Examples 1 to 15 and Comparative Examples 1 to 4 are as shown below. Further, Tables 2 to 4 below show the compositions of Examples 1 to 15 and Comparative Examples 1 to 4.

Cyclic polyolefin represented by the following formula (9) (manufactured by Mitsui Chemicals, Inc., "APL6015 (trade name)", Tg = 140, Mw = 80,000, Mw / Mn = 2.0, m: n = 58 : 42 (Molecular ratio))

Cyclic polyolefin represented by the following formula (10) (manufactured by Polyplastics Co., Ltd., "TOPAS6015 (trade name)", Tg = 140, Mw = 80,000, Mw / Mn = 2.0, m: n = 48. : 52 (Molecular ratio))

Cyclic polyolefin represented by the above formula (10) (manufactured by Polyplastics Co., Ltd., "TOPAS6017 (trade name)", norbornene content 82% by weight, Tg = 160, Mw = 80,000, Mw / Mn = 2.0, m: n = 43: 57 (molar ratio))
-Styrene-ethylene-propylene-styrene triblock copolymer (thermoplastic elastomer): SEPS (manufactured by Kuraray Co., Ltd., "Septon 2004 (trade name)", Tg = 90 ° C., styrene content 18%, molecular weight 90,000 )

The weight average molecular weight of the cycloolefin polymer used in Examples and Comparative Examples and the glass transition temperature (Tg) determined by dynamic mechanical analysis (DMA: Dynamic Mechanical Analysis) are as shown in Table 1 below. ..

The glass transition temperature (Tg (DMA) [° C.]) shown in Table 1 was set to 5 ° C./at a frequency of 1 Hz using a dynamic viscoelasticity measuring device Rheologel-E4000 (manufactured by UBM Co., Ltd.). It was determined based on the change in viscoelasticity measured by raising the temperature from 25 ° C. to 300 ° C. at a temperature rising rate of 1 minute.

In Tables 2 to 4 described later, the glass transition temperature (Tg (DMA) [° C.]) of the adhesive layers of Examples 1 to 10 and 12 to 15 was 140 ° C. for 5 minutes, and then 200. The measurement was performed under the same conditions as the glass transition temperature measured in Table 1, except that the measurement was performed after heat treatment at ° C. for 1 hour in a nitrogen atmosphere.

The glass transition temperature (Tg (DMA) [° C.]) of the adhesive layer of Example 11 was preheated at 140 ° C. for 5 minutes, and then a high-pressure mercury lamp UV exposure machine (manufactured by ORC Manufacturing Co., Ltd.). The glass transition temperature was measured under the same conditions as those shown in Table 1, except that the glass transition temperature was measured after the exposure treatment was performed under a reduced pressure vacuum under ^{the condition of 500 mJ / cm 2.}

The glass transition temperature (Tg (DMA) [° C.]) of the adhesive layers of Comparative Examples 1, 2 and 4 was the same as the glass transition temperature shown in Table 1 except that the preliminary heat treatment was performed at 160 ° C. for 5 minutes. It was measured under the same conditions as the measurement. The glass transition temperature (Tg (DMA) [° C.]) of the adhesive layer of Comparative Example 3 was the same as that of the adhesive layer of Example 1 except that the preliminary heat treatment was performed at 160 ° C. for 5 minutes. It was heat-treated and the glass transition temperature was measured.

[Curable monomer]
-Tricyclodecanedimethanol diacrylate represented by the following formula (11) (manufactured by Shin-Nakamura Chemical Co., Ltd., "A-DCP (trade name)")

・以下の式（１２）で示されるトリシクロデカンジメタノールジメタクリレート（新中村化学株式会社製、「ＤＣＰ（商品名）」）

-Tricyclodecanedimethanol dimethacrylate represented by the following formula (12) (manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP (trade name)")

1,3-adamantane diol diacrylate represented by the following formula (13) (manufactured by Mitsubishi Gas Chemical Company, Inc., "ADDA (trade name)")

-5-Hydroxy-1,3-adamantane dihydroxymethacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc., "HADDM (trade name)") represented by the following formula (14).

1,3,5-adamantane triol trimethacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc., "ADTM (trade name)") represented by the following formula (15).

[Evaluation 1: Evaluation of adaptability to sealing of elements by compression type]
The bare chips were placed at predetermined positions in the adhesive layer of Example 1, and the bare chips were sealed with a sealing agent (sealing material). The degree of misalignment of the bare chip at this time was evaluated as the adaptability to the sealing (molding) by the compression type.

The bare chips were arranged using a die bonder (manufactured by TRESKY). First, the plate of the die bonder was heated to 150 ° C., and a 2 mm square silicon bare chip was crimped onto the adhesive layer of Example 1 for 1 second at a pressure of 35 N. As a result, as shown in FIG. 5, bare chips (elements) 5 are arranged at the peripheral portions and the central portions of the four corners of the adhesive layer 3 formed on the glass support 1.

Next, the adhesive layer of Example 1 in which the bare chips were placed was heated at 200 ° C. for 1 hour in a nitrogen atmosphere. After heating, in a state where the bare chips are arranged, the glass support on which the adhesive layer of Example 1 is formed is placed on a plate heated to 50 ° C., a sealant containing 12 g of epoxy resin is placed on the glass support, and the pressure is increased from 10 Pa. Under low depressurization conditions, 1 ton of pressure was applied on a pressing plate heated to 130 ° C. and compressed for 5 minutes using a sticking device (in the arrangement step shown in FIGS. 2C and 2). Applicable). As a result, the bare chips arranged on the adhesive layer were sealed with a sealing material to obtain a laminated body of Example 1 in which the sealing substrates were laminated.

The laminate of Example 1 was observed from the glass surface side using an optical microscope, and the degree of misalignment of the attached bare chip 5 was evaluated. As shown in FIG. 5, the sum of the moving distances in the X direction and the Y direction was obtained from the position when each bare chip 5 arranged on the adhesive layer 3 was attached, and used as the moving distance of each bare chip. Subsequently, the average value of the moving distance of the bare chip 5 was obtained and used as the evaluation value of the moving distance.

The adaptability to the sealing by the compression type is evaluated as “○” without misalignment when the moving distance of the bare chip 5 is 3 μm or less, and “×” with misalignment when the moving distance of the bare chip 5 is larger than 3 μm. I evaluated it.

For the adhesive layers of Examples 2 to 10, 12 to 15, and Comparative Example 3, the adhesive layer was formed according to the same procedure as in Example 1, and the adaptability to the sealing of the element by the compression type was evaluated.

Further, the adhesive layers of Comparative Examples 1, 2, and 4 are the same as the procedure in the evaluation of the adhesive layer of Example 1 except that the adhesive layer is not heated after the bare chips are crimped to a predetermined position. , The adaptability to the sealing of the element by the compression type was evaluated.

For the adhesive layer of Example 11, after crimping the bare chip using a die bonder, a high-pressure mercury lamp UV exposure machine (manufactured by ORC Manufacturing Co., Ltd.) was used instead of the heat treatment in a nitrogen atmosphere at 200 ° C. for 1 hour. The adaptability to the sealing of the element by the compression type was evaluated in the same manner as the procedure in the evaluation of the adhesive layer of Example 1, except that the exposure treatment was performed under the condition of 500 mJ / cm ^{2 under reduced vacuum.} ..

Tables 2 to 4 below show the results of the adaptability evaluation to the sealing of the device by the compression type.

[Evaluation 2: Evaluation of adaptability to insulation pattern formation process]
The adhesive layers of Examples 1 to 15 and Comparative Examples 1 to 4 prepared according to the same procedure as the adhesive layer used in Evaluation 1 were evaluated for adaptability to the insulation pattern formation process (evaluation 2). In the evaluation of adaptability to the insulation pattern forming process, the chemical resistance to the resist solvent and the heat resistance to the heat treatment after the pattern formation were evaluated.

For Examples 1 to 10, 12 to 15 and Comparative Examples 1 to 4, the adaptability to the insulation pattern formation process was evaluated after heat treatment at 200 ° C. for 1 hour in a nitrogen atmosphere, respectively. .. Further, the adhesive layer of Example 11 was exposed under the same conditions as the exposure conditions in Evaluation 1, and then the adaptability to the insulation pattern forming process was evaluated.

(Evaluation of drug resistance)
First, regarding the evaluation of the positive resist, the insulating film forming composition PN-0379D (containing PGMEA, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated at 1000 rpm on each adhesive layer at 110 ° C. for 4 minutes. By preheating under the conditions, a dry film of 5 μm was formed. Next, a pattern exposure was performed on the coating film using a parallel light exposure machine (ghi) manufactured by ORC. Next, the exposed film was immersed in a 2.38% TMAH aqueous solution at 23 ° C. for 5 minutes to form a photosensitive insulating film with a positive resist in a line pattern having a width of 100 μm.

Regarding the evaluation of the negative resist, BL301 (containing NMP, manufactured by Asahi Kasei Corporation), which is a negative resist, was spin-coated on each adhesive layer at 1000 rpm and preheated at 110 ° C. for 4 minutes. By doing so, a 5 μm adhesive layer was formed. Next, after pattern exposure was performed using a parallel light exposure machine (ghi) manufactured by ORC, the photosensitive insulating film made of a negative resist was immersed in cyclohexanone at 23 ° C. for 5 minutes with a line pattern having a width of 100 μm. Formed.

For the evaluation of chemical resistance, changes in the appearance of each adhesive layer when the pattern obtained above was immersed in PGMEA, TMAH, NMP, and cyclohexanone at 23 ° C. for 5 minutes were visually evaluated. The chemical resistance is evaluated as "○" when there is no change in weight and appearance, and "×" when there is a change in weight or appearance (floating line pattern or presence or absence of cracks in the adhesive layer). It was judged.

Tables 2 to 4 below show the evaluation results of chemical resistance in the evaluation of adaptability to the insulation pattern formation process.

(Evaluation of heat resistance)
Next, as an evaluation of heat resistance, each laminate whose chemical resistance was evaluated was heat-treated at 200 ° C. for 4 hours in a nitrogen atmosphere, and then shrinkage occurred in a line pattern formed in a width of 100 μm. It was evaluated whether or not it was. For the evaluation of heat resistance, the width of the 100 μm width line pattern after heat treatment is measured using an optical microscope, and if the increase / decrease in width is smaller than 5 μm, it is evaluated as heat resistance “○” and the increase / decrease in width is 5 μm. If it was larger, it was evaluated as heat resistance "x".

Tables 2 to 4 below show the evaluation results of heat resistance in the evaluation of adaptability to the insulation pattern formation process.

After evaluating the heat resistance, the bare chips are placed on each adhesive layer on which the line pattern is formed, and the bare chips are sealed with a sealing agent containing an epoxy resin under the same conditions as in the evaluation 1. , A laminated body in which sealing substrates were laminated was obtained.

[Evaluation 3: Evaluation of detergency]
The separation layer was altered by irradiating a laser beam having a wavelength of 532 nm from the glass support side of each of the laminates formed in Evaluations 1 and 2 toward separation. The glass support was then separated from each laminate to expose the adhesive layer. Using p-menthane as a cleaning liquid, spray cleaning was performed for 5 minutes to clean the sealing substrate on which the adhesive layer remained. In the evaluation of detergency, the presence or absence of residue on the adhesive layer on the sealing substrate is visually confirmed, and when no residue is observed, the detergency is evaluated as "○", and when a large amount of residue is observed. Evaluated the detergency as "x".

Table 2 below shows the compositions of the adhesive compositions of Examples 1 to 6 and the evaluation results.

Table 3 below shows the compositions of the adhesive compositions of Examples 7 to 15 and the evaluation results.

Table 4 below shows the compositions of the adhesive compositions of Comparative Examples 1 to 4 and the evaluation results.

(Each evaluation result)
As shown in Tables 2 and 3, regarding the evaluation of adaptability to the sealing of the element by the compression type, no misalignment of the arranged bare chips was observed in any of the adhesive layers of Examples 1 to 15 (◯). On the other hand, as shown in Table 4, in Comparative Examples 1 to 4, the position of the bare chip was displaced (x). From these results, it was confirmed that by using a base polymer having a Tg of 140 ° C. or higher, an adhesive composition capable of sealing the element on the adhesive layer and preferably sealing the element can be obtained. We were able to.

In Table 5 below, the adhesive layer of Example 7 was evaluated for adaptability to the sealing of the element by the compression type, and the heating temperature in the pressing press was changed from 130 ° C. to 150 ° C. and 170 ° C. The results are shown.

Further, as shown in Table 5, in Comparative Example 1, a large movement of the chip (535 μm) was observed, whereas in Example 7, even if the plate temperature at the time of sealing was 170 ° C., the position of the chip was almost the same. No deviation was observed (≦ 3 μm).

Further, as shown in Tables 2 and 3, regarding the evaluation of adaptability to the sealing of the element by the compression type, no misalignment of the arranged bare chips was observed in any of the adhesive layers of Examples 1 to 15 (◯). ). On the other hand, as shown in Table 4, in Comparative Examples 1 to 4, the position of the bare chip was displaced (x). In particular, in the adhesive layer of Comparative Example 3, even if A-DCP was blended, sufficient results could not be obtained in Evaluation 1 and Evaluation 2. From the results of Examples 1 to 15 and Comparative Examples 1 to 4, by using a cycloolefin polymer having a Tg of 100 ° C. or higher and a curable monomer, it is possible to prevent deformation even when a force is applied in a high temperature environment. It was confirmed that it was possible to form an adhesive layer that could form an adhesive layer. Further, from this result, an adhesive composition capable of arranging an element on the adhesive layer and suitably sealing the element can be obtained by using a cycloolefin polymer having a Tg of 100 ° C. or higher and a curable monomer. I was able to confirm that I could do it.

Regarding the chemical resistance in the evaluation of adaptability to the insulation pattern forming process, it was confirmed that all of Examples 1 to 15 and Comparative Examples 1 to 4 had high chemical resistance to each resist solvent. However, in the evaluation of heat resistance, in the adhesive layers of Examples 1 to 15, shrinkage of the resist pattern formed on the adhesive layer was not substantially observed under the heating conditions of 200 ° C. and 4 hours (◯). On the other hand, in the adhesive layers of Comparative Examples 1 to 4, shrinkage of the resist pattern was observed (x). From these facts, it was confirmed that the adhesive layer capable of preventing the shrinkage of the resist pattern can be formed by using the cycloolefin polymer having a high Tg and the curable monomer in combination.

Further, the line pattern formed on the adhesive layer of Example 7 and Comparative Example 1 and the line pattern formed directly on the glass support without forming the adhesive layer are under the same conditions as the heat resistance evaluation in Evaluation 2. The line pattern width was increased or decreased and the amount of change was measured. The results are shown in Table 6 below.

As shown in Table 6, before and after the heat treatment in the pattern formation with the resist, the degree of shrinkage of the resist pattern formed on the adhesive layer of Example 7 and the shrinkage of the resist pattern formed directly on the glass support. It was confirmed that the degree of was almost the same.

In addition to this, in the evaluation of detergency (evaluation 3), as shown in Tables 2 to 4, the adhesive layers of Examples 1 to 15 could be satisfactorily removed by cleaning with p-menthane (◯).

From the above results, by blending a curable monomer with a cycloolefin polymer having a Tg of 100 ° C. or higher, an adhesive layer having high adaptability to the insulation pattern formation process and the insulation pattern formation process can be formed. It was confirmed that an adhesive composition capable of producing an adhesive composition can be obtained.

INDUSTRIAL APPLICABILITY The present invention can be suitably used particularly in the manufacture of semiconductor devices by fan-out type technology.

1 Support 3 Adhesive layer 4 Rewiring layer 5 Bare chip (element, sealant)
6 Encapsulant (encapsulant)
7,7'Encapsulated substrate 8,8', 9,9' Laminated body

Claims (13)

An adhesive composition for forming the adhesive layer in a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The adhesive composition contains , as a resin component, a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher , and a polyfunctional curable monomer .
The content of the polyfunctional curable monomer in the resin component is 40% by weight or less.
An adhesive composition, wherein the glass transition temperature of the adhesive layer when the adhesive layer is cured by polymerization of the polyfunctional curable monomer is 160 ° C. or higher. An adhesive composition for forming the adhesive layer in a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The adhesive composition contains , as a resin component, a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher, and a polyfunctional curable monomer.
The content of the polyfunctional curable monomer in the resin component is in the range of 10% by weight or more and 40% by weight or less.
An adhesive composition, wherein the glass transition temperature of the adhesive layer when the adhesive layer is cured by polymerization of the polyfunctional curable monomer is 160 ° C. or higher. The adhesive composition according to claim 1 or 2, wherein the polyfunctional curable monomer has a polycyclic aliphatic structure. The adhesive according to any one of claims 1 to 3 , wherein the cycloolefin polymer is an addition polymer of a constituent unit having a polycyclic aliphatic structure and an ethylene monomer unit. Composition. The claim is characterized in that it further contains a solvent for dissolving the resin component, and the solvent contains one selected from the group consisting of condensed polycyclic hydrocarbons and branched hydrocarbons. The adhesive composition according to any one of 1 to 4. An adhesive film, wherein an adhesive layer made of the adhesive composition according to any one of claims 1 to 4 is formed on the film. It is a manufacturing method of a laminated body for manufacturing a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
Forming an adhesive layer that forms the adhesive layer by applying the adhesive composition according to any one of claims 1 to 5 to at least one of the substrate or the support and heating the adhesive composition. A method for producing a laminate, which comprises a process. It is a manufacturing method of a laminated body for manufacturing a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The substrate is a sealing substrate including a sealing body in which an element is sealed with a sealing material and a rewiring layer provided on one flat surface portion of the sealing body and on which the element is mounted. ,
On the support, by coating the adhesive composition, and contacting adhesive layer forming step you forming the adhesive layer by heating,
The arrangement process of arranging the element on the adhesive layer and
After the arrangement step, a sealing step of sealing the element with a sealing material is included .
The glass transition temperature of the adhesive layer is 160 ° C. or higher, and the adhesive composition contains a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher as a resin component. Method. It is a manufacturing method of a laminated body for manufacturing a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The substrate is a sealing substrate including a sealing body in which an element is sealed with a sealing material and a rewiring layer provided on one flat surface portion of the sealing body and on which the element is mounted. ,
On the support, by coating the adhesive composition, and contacting adhesive layer forming step you forming the adhesive layer by heating,
It includes a rewiring layer forming step of forming the rewiring layer on the adhesive layer .
The glass transition temperature of the adhesive layer is 160 ° C. or higher, and the adhesive composition contains a cycloolefin polymer having a glass transition temperature of 160 ° C. or higher as a resin component. Method. It is a manufacturing method of a laminated body for manufacturing a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The substrate is a sealing substrate including a sealing body in which an element is sealed with a sealing material and a rewiring layer provided on one flat surface portion of the sealing body and on which the element is mounted. ,
An adhesive layer forming step of applying an adhesive composition onto the support and heating the support to form the adhesive layer.
The arrangement process of arranging the element on the adhesive layer and
After the arrangement step, a sealing step of sealing the element with a sealing material is included.
The adhesive composition contains, as a resin component, a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher, and a polyfunctional curable monomer.
A method for producing a laminate, wherein the glass transition temperature of the adhesive layer when the adhesive layer is cured by polymerization of the polyfunctional curable monomer is 160 ° C. or higher. It is a manufacturing method of a laminated body for manufacturing a laminated body in which a substrate, an adhesive layer, and a support are laminated in this order.
The substrate is a sealing substrate including a sealing body in which an element is sealed with a sealing material and a rewiring layer provided on one flat surface portion of the sealing body and on which the element is mounted. ,
An adhesive layer forming step of applying an adhesive composition onto the support and heating the support to form the adhesive layer.
It includes a rewiring layer forming step of forming the rewiring layer on the adhesive layer.
The adhesive composition contains, as a resin component, a cycloolefin polymer having a glass transition temperature of 100 ° C. or higher, and a polyfunctional curable monomer.
A method for producing a laminate, wherein the glass transition temperature of the adhesive layer when the adhesive layer is cured by polymerization of the polyfunctional curable monomer is 160 ° C. or higher. The support is a support made of a material that transmits light.
Any of claims 7 to 11 , further comprising a separation layer forming step of forming a separation layer that is altered by irradiation with light on the support before the adhesion layer forming step. The method for producing a laminate according to item 1. The method for producing a laminate according to claim 12,
A separation step of separating the substrate from the laminate by altering the separation layer by irradiating the separation layer with light via the support.
A substrate processing method comprising the removal step of removing the adhesive layer remaining on the substrate separated from the laminate with a cleaning liquid after the separation step.

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