JP6715142B2 - Adhesive composition and use thereof - 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) for rearranging the terminals at the end of the bare chip in the chip area and outside the chip area. Fan-out type technology such as fan-out type WLP (Fan-out Wafer Level Package) for rearranging terminals is known. In particular, the fan-out type technology is applied to a fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged on a panel for packaging, and integration, thinning and miniaturization of semiconductor devices, etc. In order to realize the above, fan-out type technologies such as these have attracted attention.

Patent Document 1 discloses an adhesive characterized by containing as a main component a polymer obtained by polymerizing a monomer composition containing (meth)acrylic acid having an adamantyl group introduced therein and hydroxystyrene. The composition is described.

Japanese Patent Laid-Open No. 2011-173956 (Published September 8, 2011)

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

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

In order to solve the above problems, the adhesive composition according to an embodiment of the present invention,
A substrate, an adhesive layer, and an adhesive composition for forming the adhesive layer in a laminate formed by laminating a support in this order,
The glass transition temperature of the adhesive layer is 190° C. or higher,
The adhesive composition contains, as a resin component, a (meth)acrylate polymer having an aliphatic polycyclic group,
The (meth)acrylate polymer is characterized in that the content of the monomer unit having an aliphatic polycyclic group is in the range of 60% by weight or more and 100% by weight or less.

The adhesive composition according to the present invention has the effect of providing a novel adhesive composition having high heat resistance, high chemical resistance, and high cleanability, and a related technique thereof.

It is a figure explaining the manufacturing method of the laminated body which concerns on Embodiment 1 of this invention, and a substrate processing method. It is a figure explaining the manufacturing method of the laminated body which concerns on Embodiment 2 of this invention, and a substrate processing method. It is a figure explaining the manufacturing method of the laminated body which concerns on Embodiment 3 of this invention, and the substrate processing method. It is a figure explaining the outline of the manufacturing method of the layered product concerning Embodiment 4 of the present invention. It is a figure explaining an outline of arrangement of an element on an adhesion layer in applicability evaluation to sealing of an element by a compression type.

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

<Adhesive composition>
An adhesive composition according to an embodiment of the present invention is an adhesive composition for forming the adhesive layer in a laminate obtained by laminating a substrate, an adhesive layer, and a support in this order, The glass transition temperature of the layer is 190° C. or higher, and the adhesive composition contains a (meth)acrylate polymer having an aliphatic polycyclic group as a resin component, and the (meth)acrylate polymer is The content of the monomer unit having an aliphatic polycyclic group is in the range of 60% by weight or more and 100% by weight or less.

The glass transition temperature of the adhesive layer formed by the adhesive composition is, as a known method, for example, dynamic mechanical analysis (Dynamic Mechanical Analysis), and at a frequency of 1 Hz, 5° C./min. It can be determined based on the change in viscoelasticity measured by increasing the temperature from 40° C. to 300° C. at the rate of temperature increase.

In addition, in this specification, unless otherwise specified, the “resin component” means a (meth)acrylate polymer and a curable monomer.

The adhesive layer formed using the adhesive composition having the above structure has high heat resistance and high chemical resistance required for forming a sealing substrate (substrate). Further, it is possible to form an adhesive layer that can preferably remove the residue of the adhesive layer after forming the sealing substrate with a solvent.

The high heat resistance of the adhesive layer formed of the adhesive composition means, 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 one embodiment of the present invention contains a (meth)acrylate polymer having an aliphatic polycyclic group having a glass transition temperature of 140°C or higher as a resin component. By containing a (meth)acrylate polymer having an aliphatic polycyclic group having a glass transition temperature of 140° C. or higher, it is suitable to use a solvent as a cleaning liquid while having high heat resistance and high chemical resistance. An adhesive layer that can be removed can be formed.

[(Meth)Acrylate Polymer Having Aliphatic Polycyclic Group]
The (meth)acrylate polymer having an aliphatic polycyclic group is a base polymer for forming an adhesive layer and contains (meth)acrylate having an aliphatic polycyclic group as a monomer unit.

In addition, in this specification, (meth)acrylate includes both the meanings of acrylate and methacrylate. Further, (meth)acrylate has a structure in which a hydrogen atom of a carboxyl group in (meth)acrylic acid is replaced with an organic group.

In addition, in the present specification, unless otherwise specified, the “(meth)acrylate polymer” means a (meth)acrylate polymer having an aliphatic polycyclic group.

The glass transition point (Tg) of the (meth)acrylate polymer having an aliphatic polycyclic group is preferably 140°C or higher, more preferably 190°C or higher, and most preferably 200°C or higher. .. If it is a (meth)acrylate polymer having a glass transition point (Tg) of 140° C. or higher, a curable monomer is blended to suitably form an adhesive layer having a glass transition temperature higher than 190° C. be able to. Moreover, as long as it is a (meth)acrylate polymer having a glass transition temperature of 190° C. or higher, a curable monomer may or may not be blended.

The weight average molecular weight of the (meth)acrylate polymer having an aliphatic polycyclic group is preferably 90,000 or more, more preferably 150,000 or more. Although not limited, the (meth)acrylate polymer having an aliphatic polycyclic group preferably has a weight average molecular weight of 1,000,000 or less. When the weight average molecular weight is 90,000 or more, it is possible to form an adhesive layer that is less likely to cause cracks after application.

(Monomer unit)
The (meth)acrylate polymer contains, as a monomer unit, at least a (meth)acrylate monomer unit having an aliphatic polycyclic group. The (meth)acrylate polymer contains, as other monomer units, a (meth)acrylate monomer unit other than the (meth)acrylate having an aliphatic polycyclic group, and a monomer unit having an aromatic group. You may stay.

The aliphatic polycyclic group contained in the (meth)acrylate monomer unit includes, for example, an aliphatic polycyclic group having a polycycloalkane structure such as a dicycloalkane structure, a tricycloalkane structure or a tetracycloalkane structure. A cyclic group etc. can be illustrated. More specifically, there may be mentioned dicycloalkane structures such as norbornane and isobornane, tricycloalkane structures such as adamantane and tricyclodecane, and tetracycloalkane structures such as tetracyclododecane. Above all, an aliphatic polycyclic group having a tricycloalkane structure and a tetracycloalkane structure is more preferable. Further, in the aliphatic polycyclic group, at least one hydrogen atom may be substituted with, for example, a hydroxyl group, an alkyl group or the like. Moreover, the (meth)acrylate polymer having an aliphatic polycyclic group may have two or more kinds of aliphatic polycyclic groups.

Examples of the (meth)acrylate unit having an adamantane structure include 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl ( Examples thereof include (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, and 3-hydroxy-1-adamantyl (meth)acrylate. Examples of the (meth)acrylate having an isobornane structure include isobornyl (meth)acrylate.

In the (meth)acrylate polymer having an aliphatic polycyclic group, the content of the (meth)acrylate monomer unit having an aliphatic polycyclic group is preferably 60% by weight or more and 100% by weight or less, 70 It is more preferable that the content is not less than 100% by weight and not more than 100% by weight. When the content of the (meth)acrylate monomer unit having an aliphatic polycyclic group is within the above range, it is possible to provide an adhesive layer that can be suitably washed and removed while exhibiting high heat resistance.

Further, examples of the other (meth)acrylate monomer unit contained in the (meth)acrylate polymer having an aliphatic polycyclic group include an alkyl(meth)acrylate monomer. The alkyl (meth)acrylate monomer is preferably a (meth)acrylate monomer having 1 to 20 carbon atoms in the alkyl group, and more preferably a (meth)acrylate monomer having 4 to 18 carbon atoms. The alkyl group in the alkyl (meth)acrylate monomer may be linear, branched or monocyclic. Examples of the (meth)acrylate monomer having an alkyl group include stearyl (meth)acrylate and lauryl (meth)acrylate. Further, the monomer unit having an aromatic group typically includes styrene. These monomer units may be used alone or in combination of two or more kinds.

There are no particular restrictions on the polymerization method and the polymerization conditions when the monomer units are polymerized, and they may be appropriately set according to a conventional method.

[Polyfunctional curable monomer]
The adhesive composition contains, as a resin component, in addition to a (meth)acrylate polymer having an aliphatic polycyclic group, a polyfunctional type compound compatible with the (meth)acrylate polymer having an aliphatic polycyclic group. It may contain a curable monomer. As a result, even when the (meth)acrylate polymer having an aliphatic polycyclic group having a glass transition temperature of 140° C. or higher is used, adhesion of the glass transition temperature higher than 190° C. is achieved by polymerizing the curable monomer. Layers can be formed. The curable monomer is preferably a monomer that is polymerized by a radical polymerization reaction, and typically, a polyfunctional (meth)acrylate monomer can be mentioned.

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, polypropylene glycol di( (Meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, tricyclodecane di Methanol di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, propoxylated bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di (Meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2-hydroxy -3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin tri(meth) ) Acrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (that is, tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, and the like. To be 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 an aliphatic polycyclic group. When the curable monomer has a cyclic structure, more preferably an aliphatic polycyclic group, compatibility with the (meth)acrylate polymer having an aliphatic polycyclic group can be increased. In addition, the heat resistance of the adhesive layer can be further increased by polymerizing the curable monomer mixed with the (meth)acrylate 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-adamantanediol di(meth)acrylate, 5- Hydroxy-1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth) At least one selected from the group consisting of acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, and propoxylated bisphenol A di(meth)acrylate is more preferable.

The content of the curable monomer may be determined in consideration of the glass transition temperature of the (meth)acrylate polymer. For example, if the glass transition temperature of the (meth)acrylate polymer contained as a resin component in the adhesive composition is 140° C. or higher, the content of the curable monomer is 1% by weight with the total of the resin components being 100% by weight. % Or more and 30% by weight or less is preferable, and 1% by weight or more and 10% by weight or less is more preferable. When the content of the curable monomer is 1% 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 30% by weight or less, the cleaning property when the adhesive layer is removed by the cleaning liquid can be improved. In other words, the content of the curable monomer can be reduced to 30% by weight or less by using the (meth)acrylate polymer having a glass transition temperature of 140° C. or higher, whereby the curable monomer is cured. It is possible to prevent deterioration of the cleaning property of the adhesive layer. Therefore, the content of the curable monomer can be reduced as the (meth)acrylate polymer having a higher glass transition temperature is used. In particular, when the glass transition temperature of the (meth)acrylate polymer is 190° C. or higher, it is possible to obtain an adhesive composition capable of forming an adhesive layer having high heat resistance without adding a curable monomer.

(Polymerization initiator)
The adhesive composition according to one embodiment may further include a polymerization initiator that accelerates 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 polymerization initiators.

Examples of peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides and peroxyesters. Specifically, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butyl cumyl 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, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1. -Hydroperoxide, tert-butyl pertriphenylacetate, tert-butyl hydroperoxide, tert-butyl formate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, per-4-methoxyacetic acid Examples include tert-butyl, tert-butyl perN-(3-toluyl)carbamate, and the like.

As commercially available peroxides, for example, trade name “Park Mill (registered trademark)”, trade name “Perbutyl (registered trademark)”, trade name “Perloyl (registered trademark)”, and trade name manufactured by NOF CORPORATION The name "Perocta (registered trademark)" and the like can be mentioned.

Examples of the azo-based 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'-azobisisobutyramide, 2,2' -Azobisisobutyronitrile, methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, Dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis(sodium 1-methylbutyronitrile-3-sulfonate), 2-(4-methylphenylazo)-2-methylmalonodinitrile 4,4' -Azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid 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 Heptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 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-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyethoxy)phenyl. ]-2-Hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2 -Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio )Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone 1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethyl Aminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, Benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 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, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidal, 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 (that is, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (that is, ethylmich Razketone), 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, p-t-butylacetophenone, p-dimethylaminoacetophenone, p-t -Butyltrichloroacetophenone, pt-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9- Phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4 ,6-Tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4 ,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4- Diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)- s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-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 include trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. To be Further, as the photopolymerization initiator, commercially available products “IRGACURE OXE02”, “IRGACURE OXE01”, “IRGACURE 369”, “IRGACURE 651” and “IRGACURE 907” (trade names: all manufactured by BASF) and “NCI-”. 831" (trade name: manufactured by ADEKA) or 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 0.5 parts by weight or more and 5 parts by weight or less. More preferable. However, when the adhesive composition does not contain a curable monomer, the polymerization initiator is not an essential component.

The polymerization initiator can be added to the adhesive composition by a known method. Further, the polymerization initiator may be added to the adhesive composition after being diluted with an addition solvent described below.

(Thermal polymerization inhibitor)
In the present invention, the adhesive composition may contain a 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 is possible that the (meth)acrylate polymers are polymerized by reacting with each other preferentially over the (meth)acrylate polymer and the curable monomer. Ban. Therefore, it is possible to prevent the solubility of the adhesive layer in the cleaning liquid from being lowered by heating the adhesive layer formed of the adhesive composition.

The thermal polymerization inhibitor is not particularly limited as long as it is effective in preventing 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, it is possible to use a hindered phenol-based antioxidant, for example, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, Amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4′-(1-methylethylidene)bis(2-methylphenol), 4,4′-(1-methylethylidene)bis(2,6 -Dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4,4',4"-ethylidenetris(2- Methylphenol), 4,4′,4″-ethylidene trisphenol, 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- (3,5-Di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythryltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX1010, BASF Corporation Manufactured), 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 depending on the type of (meth)acrylate polymer, the type of curable monomer compatible with the polymer, and the application and use environment of the adhesive composition. When the amount of the (meth)acrylate 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 the polymerization is satisfactorily exhibited, and the decrease in the solubility of the adhesive composition in the stripping solution after the high temperature process can be further suppressed.

(Additional solvent)
It is preferable that the polymerization initiator and the polymerization inhibitor are dissolved in an additive solvent and added to 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, each component of the adhesive composition can be dissolved to form a uniform solution, and only one organic solvent may be used, or two or more organic solvents may be used in combination. Good.

Specific examples of the organic solvent include, for example, oxygen atom as a polar group, a terpene solvent having a carbonyl group or an acetoxy group, and the like, for example, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonone, tsuyon, There is camphor. Further, lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone and other ketones; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol. Compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monomethyl ethers of the above polyhydric alcohols or compounds having an ester bond such as , Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers such as monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monomethyl ether (PGME) is preferred); 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, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether and the like can be mentioned.

The content of the added solvent may be appropriately adjusted according to the type of the polymerization initiator and the polymerization inhibitor, and for example, the total of the diluent solvent (main solvent) that dissolves the resin component and the added solvent is 100 parts by weight. In this case, the content of the added 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 added solvent is within the above range, the thermal polymerization initiator and the photopolymerization initiator can be sufficiently dissolved.

(solvent)
The solvent (main solvent) contained in the adhesive composition according to the present invention may be one having a function of dissolving the (meth)acrylate polymer and the (meth)acrylate monomer which is a curable monomer, and for example, a non-solvent may be used. A polar hydrocarbon solvent, a polar or 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 a condensed polycyclic hydrocarbon or a branched hydrocarbon, it is possible to avoid clouding that may occur when the adhesive composition is stored in a liquid form (especially at low temperature). It is preferable because the product stability can be improved.

Examples of the hydrocarbon-based solvent include linear, branched or cyclic hydrocarbons. For example, linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane, etc., branched hydrocarbons having 4 to 15 carbon atoms such as isooctane, isononane, isododecane; p-menthane , O-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornan, norbornane, pinan, tsujang, karan, longifolene and other saturated aliphatic hydrocarbons, α-terpinene, β-terpinene , Γ-terpinene, α-pinene, β-pinene, α-Tujone, β-Tujone and the like.

The petroleum solvent is a solvent that is refined from heavy oil, and examples thereof include white kerosene, paraffinic solvent, and isoparaffinic solvent, which may be a mixture of the above linear, branched, or cyclic hydrocarbons. .. In addition, the petroleum solvent may contain 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.

In addition, examples of the alicyclic hydrocarbon include condensed polycyclic hydrocarbons. A condensed polycyclic hydrocarbon is a condensed ring hydrocarbon formed by two or more monocycles supplying only one side of each ring, and is a hydrocarbon formed by condensing two monocycles. It is preferable to use.

Such hydrocarbons include combinations of 5 and 6 membered rings, or combinations of 2 6 membered rings. Examples of the hydrocarbon having a combination of a 5-membered ring and a 6-membered ring include indene, pentalene, indane and tetrahydroindene, and examples of the hydrocarbon having a combination of two 6-membered rings include naphthalene and tetrahydronaphthalene ( Tetralin) and decahydronaphthalene (decalin) and the like.

As the branched hydrocarbon, for example, in addition to the above-mentioned isooctane, isononane, isododecane, etc., for example, an isoparaffin-based petroleum solvent such as “ISOPAR (trade name)” manufactured by ExxonMobil Chemical Co., Ltd. Are listed.

Further, when the solvent contains the condensed polycyclic hydrocarbon, or a branched hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon, or a branched hydrocarbon, for example, It may contain other components such as saturated aliphatic hydrocarbons. 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, based on 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 based on the entire hydrocarbon solvent, high solubility in the resin can be exhibited. If 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 can be alleviated.

The content of the solvent in the adhesive composition of the present invention may be appropriately adjusted according to the thickness of the adhesive layer formed using the adhesive composition, for example, the adhesive composition When the total amount is 100 parts by weight, the range is preferably 20 parts by weight or more and 90 parts by weight or less. When the content of the solvent is within the above range, viscosity adjustment becomes easy.

<Adhesive film>
The adhesive film according to one embodiment of the present invention has an adhesive layer made of the adhesive composition according to one embodiment of the present invention formed on the film. By using such an adhesive film, an adhesive layer can be preferably formed on the support. Therefore, an adhesive film formed using the adhesive composition according to one embodiment is also included in the scope of the present invention.

As a method for forming the adhesive layer on the film, depending on the desired film thickness and uniformity of the adhesive layer, using a known method, the dry film thickness of the adhesive layer on the film is 10 to 1, 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 excellent film thickness uniformity and surface smoothness can be formed as compared with the case where the adhesive composition is directly applied on the support to form the adhesive layer. can do.

As the film used in the production of the adhesive film, as long as it is a release film capable of peeling the adhesive layer formed on the film from the film, the adhesive layer can be transferred to the 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 used. It is preferable that the above-mentioned film is subjected to a release treatment so that transfer is easy, if necessary.

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 from the adhesive layer, but for example, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are preferable. In addition, each protective film is preferably coated with silicone or baked to facilitate the peeling from the adhesive layer.

The method of using the adhesive film is not particularly limited. For example, when a protective film is used, the protective film is peeled off, the exposed adhesive layer is stacked on the support, and A method may be mentioned in which the adhesive layer is thermocompression-bonded to the surface of the support by moving the heating roller from the surface on which the agent layer is formed).

The protective film separated 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]
The laminate has an adhesive layer having high heat resistance, high chemical resistance, and high washability formed by applying the adhesive composition according to one embodiment onto a support. On the adhesive layer, the laminate has a sealing substrate including a sealing body that seals an element with a sealing material and a rewiring layer on one flat surface of the sealing body. That is, the laminated body is a laminated body manufactured in the process of manufacturing the sealing substrate based on the fan-out type technology in which the terminals provided on the element are mounted on the rewiring layer extending outside the chip area.

[Sealing substrate]
The sealing substrate (substrate) 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 redistribution layer is also called an RDL (Redistribution Layer) and is a thin film wiring body that constitutes a wiring connected to an element, and may have a single-layer or multi-layer structure. In one embodiment, the redistribution layer includes a dielectric (eg, silicon oxide (SiO _x ), a photosensitive resin such as photosensitive epoxy, etc.) and a conductor (eg, aluminum, copper, titanium, nickel, gold, and silver). However, the wiring is not limited to this.

(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 becomes a semiconductor device.

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

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

As the material of the support, for example, glass, silicon, acrylic resin, or the like can be used, but the material is not limited to these. The shape of the support may be, for example, a support having a rectangular shape or a circular shape, but is not limited thereto.

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

The thickness of the adhesive layer may be appropriately set depending on the types of the support and the sealing substrate, the treatment performed when the sealing substrate is formed, and the like, but is preferably 0.1 μm or more and 50 μm or less. It is preferably 1 μm or more and 10 μm or less. When the thickness is 1 μm or more, the sealing substrate can be preferably fixed on the support. When the thickness is 10 μm or less, it is possible to easily remove the adhesive layer in a later step.

[Separation layer]
The separation layer is a layer that is altered by being irradiated 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 the present specification, the term “degenerate” of the separation layer means a phenomenon in which the separation layer can be broken by receiving a slight external force, or a state in which the adhesive force between the separation layer and a layer in contact with the separation layer is reduced. To do. As a result of the alteration of the separation layer caused by absorbing light, the separation layer loses its strength or adhesiveness before being exposed to light. That is, by absorbing light, the separation layer becomes brittle. The alteration of the separation layer may mean that the separation layer undergoes decomposition due to the energy of the absorbed light, changes in the configuration, dissociation of functional groups, or the like. Degradation 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 stacked body is fixed to the mounting table by a support separation device or the like, and the other is held and lifted by a suction pad (suction unit) or the like equipped with suction means. By separating the support plate and the substrate, or by applying force to the chamfered portion of the peripheral edge of the support plate by a separation plate equipped with a clamp (claw), a force is applied to the substrate and the support plate. It is good to separate and. Further, for example, the support plate may be peeled from the substrate in the laminated body by a support separation device equipped with a peeling unit that supplies a peeling liquid for peeling the adhesive. By supplying the peeling liquid to at least a part of the peripheral edge portion of the adhesive layer in the laminate by the peeling means to swell the adhesive layer in the laminate, the force concentrates from the swelled portion of the adhesive layer to the separation layer. In this way, a force can be applied to the substrate and the support plate. Therefore, the substrate and the support plate can be preferably separated.

The force applied to the laminated body may be appropriately adjusted according to the size of the laminated body and the like, and is not limited. For example, for 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 preferably separated.

The thickness of the separation layer is, for example, 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, desired deterioration can be caused in the separation layer by short-time light irradiation and low-energy light irradiation. Further, the thickness of the separation layer is particularly preferably 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 layers may be made of a material that transmits light. With this, it is possible to appropriately add a layer having preferable properties and the like without hindering the incidence of light on the separation layer. The wavelength of light that can be used differs depending on the type of material forming the separation layer. Therefore, the material forming the other layers does not need to transmit all the light, and can be appropriately selected from materials capable of transmitting light having a wavelength that can change the quality of the material forming the separation layer.

Further, the separation layer is preferably formed only of a material having a structure that absorbs light, but within a range that does not impair the essential characteristics of the present invention, a material that does not have a structure that absorbs light is used. 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 is evenly attached. It becomes possible.

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

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

The light for irradiating the separation layer may be a solid laser such as YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser or fiber laser, or liquid laser such as dye laser, depending on the wavelength that can be absorbed by fluorocarbon. , CO ₂ laser, excimer laser, Ar laser, gas laser such as He—Ne laser, semiconductor laser, laser light such as free electron laser, or non-laser light may be used as appropriate. The wavelength that can change the quality of the fluorocarbon is not limited to this, but a wavelength in the range of 600 nm or less can be used, for example.

(A polymer containing a light absorbing structure in its repeating unit)
The separation layer may contain a polymer having a light absorbing structure in its repeating unit. The polymer is deteriorated by being irradiated with light. The alteration of the polymer occurs due to the structure absorbing the irradiated light. The separation layer loses its strength or adhesiveness prior to being exposed to light as a result of the alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is destroyed and the support and the sealing substrate can be easily separated.

The above structure having a light absorbing property is a chemical structure that absorbs light and changes the polymer containing the structure as a repeating unit. The structure is, for example, an atomic group containing a conjugated π-electron system consisting of a substituted or unsubstituted benzene ring, a condensed ring or a heterocycle. More specifically, the structure may be a cardo structure, or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), a diphenyl structure or a diphenylamine structure existing in the side chain of the polymer.

When the structure is present on the side chain of the polymer, the structure may be represented by the 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, each 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 ), where R ⁴ and R ⁵ each independently, a is), Z is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, absent or -CO is _-, - SO 2 -, - a SO- or -NH-, n is It is 0 or an integer of 1 to 5.)
Further, the above-mentioned polymer contains, for example, a repeating unit represented by any one of (a) to (d) in the following formulas, is represented by (e), or is represented by (f). It contains the structure in its backbone.

（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 0 or an integer of 1 to 2, and X is any one of the formulas shown in the above "Chemical formula 1" in (a) to (e). Yes, in any one of the formulas shown in the above “Chemical formula 1” in (f) or does not exist, Y ₁ and Y ₂ are each independently —CO— or SO ₂ —. Is preferably an integer of 10 or less.)
Examples of the benzene ring, the condensed ring and the heterocycle shown in the above “Chemical Formula 1” include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted Examples include acridine, azobenzene, substituted azobenzene, fluorimme, substituted fluorimme, fluorimone, substituted fluorimone, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene and substituted pyrene. When the exemplified substituent further has a substituent, the substituent is, 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 shown in the above “Chemical formula 1”, the fifth substituent having two phenyl groups, wherein Z is —SO ₂ — is exemplified by 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 the above “Chemical formula 1”, the fifth substituent having two phenyl groups, and the case where Z is —SO— is, for example, 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(2,2 4,6-trihydroxyphenyl) sulfoxide, bis(5-chloro-2,4,6-trihydroxyphenyl) sulfoxide and the like can be mentioned.

Among the substituents shown in the above “Chemical formula 1”, the fifth substituent having two phenyl groups, wherein Z is —C(═O)—, is exemplified by 2 ,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'- Methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2',4'-dihydroxybenzophenone, 4-dimethylamino-3',4'-dihydroxybenzophenone and the like can be mentioned.

When the structure is present in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is such that the light transmittance of the separation layer is 0.001% or more and 10% or more. It is within the following range. When the polymer is prepared so that the ratio falls within such a range, the separation layer can sufficiently absorb light and be surely and rapidly deteriorated. 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 above structure can absorb light having a wavelength in a desired range depending on the selection of its type. 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, within the range of 100 nm or more and 500 nm or less. For example, the structure may alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength in the range of about 300 nm to 370 nm.

Light that can be absorbed by the structure is, 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), an F2 excimer laser (wavelength: 157 nm). , XeCl laser (wavelength: 308 nm), XeF laser (wavelength: 351 nm) or solid-state UV laser (wavelength: 355 nm), g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) or i-line ( Wavelength: 365 nm) and the like.

Although the separation layer described above contains a polymer containing the above structure as a repeating unit, the separation layer may further contain components other than the above polymer. Examples of the component include a filler, a plasticizer, and a component capable of improving the releasability of the support. These components are appropriately selected from conventionally known substances or materials that do not prevent or accelerate the absorption of light by the above structure and the alteration of the polymer.

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

The above-mentioned inorganic substance may have any constitution as long as it is transformed 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 consisting of Note that carbon is a concept that can also include an allotrope of carbon, and can be, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, or the like.

The inorganic substance absorbs light having a wavelength in a specific range depending on its type. By irradiating the separation layer with light having a wavelength in the range that the inorganic material used for the separation layer absorbs, the above-mentioned inorganic material can be suitably altered.

The light for irradiating the separation layer made of an inorganic substance may be, for example, a solid-state laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, or a dye laser, depending on the wavelength that can be absorbed by the inorganic substance. Liquid laser such as CO ₂ laser, gas laser such as CO ₂ laser, excimer laser, Ar laser, He—Ne laser, semiconductor laser, laser light such as free electron laser, or non-laser light may be used as appropriate.

The separation layer made of an inorganic material can be formed on the support by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer made of an inorganic material is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used, but for example, the thickness may be in the range of 0.05 μm or more and 10 μm or less. More preferable. In addition, an adhesive may be applied in advance to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material that constitutes the separation layer and then attached to the support.

When a metal film is used as the separation layer, laser reflection or film charging may occur depending on conditions such as the quality of the separation layer, the type of laser light source, and laser output. Therefore, it is preferable to take measures against them by providing an antireflection film or an antistatic film above or below the separation layer or one of them.

(Compound having 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 adhesion before being exposed to infrared radiation as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support), the separation layer is destroyed and the support and the sealing substrate can be easily separated.

Examples of the compound having an infrared absorbing structure or a structure having an infrared absorbing property include, for example, alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, Cyclic), alkynes (mono-substituted, di-substituted), monocyclic aromatics (benzene, mono-substituted, di-substituted, tri-substituted), alcohols and phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated) Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, dialkylcarbonyl, Aromatic carbonyl, 1,3-diketone enol, o-hydroxyaryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylate anion), formate ester, acetate ester, conjugated ester, non-conjugated ester, Aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride (conjugated, non-conjugated, cyclic, acyclic), primary amide, Secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary Secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, isocyanic acid ester, thiocyanic acid ester, aliphatic isothiocyanic acid ester, aromatic isothiocyanic acid Ester, aliphatic nitro compound, aromatic nitro compound, nitramine, nitrosamine, nitrate ester, nitrite ester, nitroso bond (aliphatic, aromatic, monomer, dimer), mercaptan and thiophenol and thiol acid etc. Sulfur compounds, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary sulfonamides, secondary sulfonamides, sulfuric acid esters, carbon-halogen bonds, Si-A ¹ bonds (A ¹ is H, C, O or halogen), ^{P-A 2} bonds ^{(A 2} are, H, may be C or O), or Ti-O bonds.

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

As a structure including the ^{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, and SiF _3, and the like. As a structure containing a Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

The structure including the ^{P-A 2} _{binding, PH, PH 2, P-} CH 3, P-CH 2 -, P-C 6 H 5, A 3 3 -P-O (A 3 are aliphatic or aromatic _{^{family), (A 4 O) 3}} -P-O (A 4 _{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 above structure can absorb infrared rays having a wavelength in a desired range depending on the selection of its type. 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 can be more preferably absorbed in the range of 2 μm or more and 15 μm or less. Furthermore, when the structure is a Si—O bond, a Si—C bond, and a Ti—O bond, it may 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 each structure can absorb. For example, as an absorption band in each structure, non-patent document: SILVERSTEIN, BASLER, MORILL, "Identification method by spectra of organic compounds (5th edition)-combination of MS, IR, NMR, and UV-" (published in 1992) Reference can be made to the descriptions on pages 146 to 151.

As the compound having an infrared absorbing structure used for forming the separation layer, among the compounds having the above-mentioned structures, the compound can be dissolved in a solvent for coating and solidified to form a solid layer. It is not particularly limited as long as it can form However, in order to effectively modify the compound in the separation layer and facilitate the separation of 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 of the separation layer is preferably lower than 90%, more preferably the infrared transmittance of lower than 80%.

For example, as a compound having a siloxane skeleton, for example, 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 that 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 hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms.)
Among them, as a compound having a siloxane skeleton, a t-butylstyrene (TBST)-dimethylsiloxane copolymer, which is a copolymer of the repeating unit represented by the above chemical formula (1) and the repeating unit represented by the following chemical formula (3), is used. 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 more 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 to 10 carbon atoms, and in the chemical formula (5), R ⁸ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. It is.)
Examples of the compound having a silsesquioxane skeleton include JP-A 2007-258663 (published on October 4, 2007) and JP-A 2010-120901 (published on June 3, 2010). Each silsesquioxane resin disclosed in JP-A-2009-263316 (published on November 12, 2009) and JP-A-2009-263596 (published on November 12, 2009) is preferably used. 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 a compound having the following chemical formula (6) A copolymer containing a repeating unit represented by the following formula 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, or a cage structure, but may have any structure.

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and titanium-i-propoxyoctyleneglycolate. (ii) di -i- propoxy bis (acetylacetonato) titanium, and propane di oxytitanium bis (ethylacetoacetate) chelate titanium such as; alkoxy titanium etc. _{(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 (O-n-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 Carbonylbenzoyloxy)tributoxy titanium and the like acylate titanium; and (v) di-n-butoxy bis(triethanolaminato) titanium and other water-soluble titanium compounds.

Among them, as the compound containing a Ti-O bond, di -n- butoxy bis (triethanolaminato) titanium _{(Ti (OC 4 H 9)} 2 [OC 2 H 4 N (C 2 H 4 OH) 2] ₂ ) is preferred.

Although the separation layer described above contains a compound having an infrared absorbing structure, the separation layer may further contain a component other than the above compound. Examples of the component include a filler, a plasticizer, and a component capable of improving the releasability of the support. These components are appropriately selected from conventionally known substances or materials that do not prevent or accelerate the absorption of infrared rays by the above structure and the deterioration of the compound.

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

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

(Reactive polysilsesquioxane)
The separation layer can be formed by polymerizing a 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 polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. Oxane, which can be polymerized with each other by condensing the silanol group or a functional group capable of forming the silanol group. Further, the reactive polysilsesquioxane has a silsesquioxane skeleton such as a random structure, a cage structure, and a ladder structure if it has a silanol group or a functional group capable of forming a silanol group. Reactive polysilsesquioxanes can be employed.

Further, the reactive polysilsesquioxane more preferably 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 an alkyl group having 1 to 10 carbon atoms, and R″ is selected from the group consisting of hydrogen and an alkyl group having 1 to 5 carbon atoms. More preferably, R″ is hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms, and the reactive polysilsesquioxy group represented by the chemical formula (8) is heated by heating in the separation layer forming step. Sun can be suitably condensed.

In 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. The reactive polysilsesquioxane has a repeating unit represented by the chemical formula (8), so that it has a higher Si—O bond content than that formed by using other materials, and infrared rays (0.78 μm or more). , 1,000 μm or less), preferably far infrared rays (3 μm or more and 1,000 μm or less), and more preferably a wavelength of 9 μm or more and 11 μm or less.

Further, in the chemical formula (8), R's are independently the same or different organic groups. 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, the alkyl group may be a linear, branched or cyclic alkyl group. When R is an alkyl group, it preferably has 1 to 15 carbon atoms, and more preferably 1 to 6 carbon atoms. When R is a cyclic alkyl group, it may be an alkyl group having a monocyclic structure or a 2-4 cyclic structure.

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

Moreover, a hydroxyl group, an alkoxy group, etc. can be mentioned as a substituent which R'may have. When the substituent is an alkoxy group, a linear, branched or cyclic alkylalkoxy group can be mentioned, and the alkoxy group preferably has 1 to 15 carbon atoms, and 1 to 10 carbon atoms. Is more preferable.

Further, in one aspect, 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. .. If the siloxane content of the reactive polysilsesquioxane is 70 mol% or more and 99 mol% or less, it is preferable to irradiate 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 transformed into

In one aspect, 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, the reactive polysilsesquioxane can be suitably dissolved in a solvent and can be suitably coated on the support plate.

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

<Method for manufacturing laminated body and method for treating substrate>
A method for manufacturing a laminated body according to one embodiment (Embodiment 1) of the present invention includes a rewiring layer on which an element is mounted, and a sealing body obtained by sealing the element with a sealing material. A method for producing a laminate, which comprises laminating a substrate on a support for supporting the sealing substrate via an adhesive layer, wherein the adhesive composition described above is applied onto the support. It includes an adhesive layer forming step of forming an adhesive layer. Further, in the method for manufacturing a laminated body according to the present embodiment, the support is a support made of a material that transmits light, and is modified by irradiating the support with light before the adhesive layer forming step. And a separation layer forming step of forming a separation layer.

In addition, the substrate processing method according to the present embodiment is a method for manufacturing a laminated body according to an embodiment of the present invention, and after the laminated body is manufactured, the separation is performed by irradiating light through the support. It includes a separation step of separating the support from the laminate by modifying the layer, and a removal step of removing the residue of the adhesive layer remaining on the sealing substrate side by a cleaning liquid after the separation step. ..

FIG. 1 is a diagram for explaining each step in the method for manufacturing a laminated body and the substrate processing method according to the first embodiment of the present invention. In the method for manufacturing a laminated body according to this embodiment, the separation layer forming step, the adhesive layer forming step, and the sealing substrate forming step are performed 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 which is altered by the above is formed. The “one flat surface portion” refers to one of the flat surface portions of the support 1. In addition, the “planar portion” may have minute irregularities that can be regarded as a substantially flat surface.

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

When the adhesive layer contains a photopolymerization initiator, the curable monomer contained in the adhesive layer may be polymerized by exposing in an atmosphere of an inert gas such as nitrogen gas. The exposure conditions may be set appropriately 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 perform heating or exposure after removing the solvent.

[Sealing substrate forming process]
As shown in FIGS. 1C to 1F, in the sealing substrate forming step, the sealing substrate 7 is formed on the adhesive layer 3. In the encapsulation substrate forming process of this embodiment, a rewiring layer forming process, a mounting process, a sealing process, and a thinning process are performed in this order.

[Rewiring layer formation process]
As shown in FIG. 1C, 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 redistribution 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 deposition method, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin by a method such as spin coating, dipping, roller blade, spray coating and slit coating.

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

In this way, the adhesive layer 3 dissolves the acid such as hydrofluoric acid, the alkali such as tetramethylammonium hydroxide (TMAH), and the resist agent when the photolithography process and the etching process are performed. Exposed to the resist solvent. As the resist solvent, PGMEA, cyclopentanone, N-methyl-2-pyrrolidone (NMP), cyclohexanone and the like are used. However, the adhesive layer 3 is formed of a (meth)acrylate polymer having an aliphatic polycyclic group having a glass transition temperature of 190° C. or higher, or a (meth)acrylate polymer having an aliphatic polycyclic group. It is formed by polymerizing a curable monomer therein. Therefore, the adhesive layer 3 has high chemical resistance and can prevent the adhesive layer 3 from being dissolved or peeled off by being exposed to not only acid and alkali but also these resist solvents. .. Therefore, a highly accurate pattern can be formed on the adhesive layer 3 with the resist agent, and the redistribution layer 4 can be formed appropriately.

In the rewiring layer forming step, for example, in order to cure the resist agent formed on the adhesive layer 3, heat treatment is performed for about 4 hours under a high temperature environment of 200 to 230°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 is possible to suitably prevent 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 preferably 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 redistribution layer 4 by using, for example, a chip mounter or the like. In the mounting step, if the element 5 is mounted on the rewiring layer 4 via the solder bump, the solder bump may be sealed by underfill before sealing the element 5. ..

As shown in FIG. 1E, 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 by using a molding die while maintaining a high viscosity state in a state of being heated to 130° C. to 170° C., for example. Therefore, when the element 5 is sealed with the sealing material 6, the adhesive layer 3 is pressed at a temperature of 130° C. to 170° C. in the state where the element 5 is 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 pressed at a temperature of 130° C. to 170° C. You can

As shown in FIG. 1F, in the thinning step, the sealing material 6 is thinned. The sealing material 6 may be thinned to a thickness equivalent to that of the element 5, for example.

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

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

[Separation process]
As shown in (h) of FIG. 1, in the separation step, the separation layer 2 is irradiated with light L through the support 1 to change the quality of the separation layer 2. The type and wavelength of the light L to be irradiated may be appropriately selected depending on the transparency of the support 1 and the material of the separation layer 2, and examples thereof include YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber. A solid laser such as a laser, a liquid laser such as a dye laser, a CO ₂ laser, an excimer laser, an Ar laser, a gas laser such as a He—Ne laser, a semiconductor laser, a laser light such as a free electron laser, or a non-laser light is used. 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.

The following conditions can be given as examples of the laser light irradiation conditions when the laser light is irradiated, but are not limited thereto: The average output value of the laser light is 1.0 W or more and 5.0 W or less. Is preferable, and more preferably 3.0 W or more and 4.0 W or less; the repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. It is preferable; the scanning speed of the laser light is preferably 100 mm/s or more and 10,000 mm/s or less.

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

[Removal process]
As shown in (h) of FIG. 1, in the removal step, the adhesive layer 3 and the separation 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 containing an organic solvent or the like 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 carbonization such as tetrahydronaphthalene. More preferably, hydrogen is used.

As described above, the isolated sealing substrate 7 can be obtained.

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

[Embodiment 2]
The following will describe another embodiment of the present invention. For convenience of description, members having the same functions as the members described in the above embodiment will be designated by the same reference numerals, and the description thereof will be omitted. The method for manufacturing a laminate and the method for treating a substrate according to the second embodiment include a separation layer forming step, an adhesive layer forming step, a sealing substrate forming step, a separating step, and a removing step in this order, and a sealing substrate forming step. Then, the element is arranged on the adhesive layer 3. Note that, as shown in FIG. 2A, the separation layer forming step is the same as that of the first embodiment, and therefore its description is omitted.

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

[Sealing 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 encapsulation substrate forming process in the present embodiment, the disposing process, the encapsulating process, the thinning process, and the rewiring layer forming process are performed in this order.

As shown in FIG. 2C, in the placement step, the element 5 is placed on the adhesive layer 3. More specifically, in the arranging step, the support 5 on which the adhesive layer 3 is formed is heated to about 100° C., and the element 5 is pressure-bonded 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 increased by heating the adhesive layer 3 after the element 5 is placed on the adhesive layer 3 in the placement step. It is advisable to polymerize the monomers. When the adhesive layer contains a photopolymerization initiator, the adhesive layer 3 may be exposed to cure.

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 sealing the element 5 with the sealing material 6, the adhesive layer 3 is pressed at a temperature of 130° C. to 170° C. with the element 5 arranged. To 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 pressed by the sealing material 6 under the temperature condition of 130° C. to 170° C. The shift can be prevented. 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. 2E, in the thinning step, the sealing material 6 is thinned. The sealing material 6 may be thinned, for example, until the terminal portion of the element 5 is exposed from the sealing material 6.

As shown in FIG. 2F, in the rewiring layer forming step, the rewiring layer 4 is formed on the plane portion of the sealing body where the element 5 is exposed.

In the present embodiment, the rewiring layer 4 can be formed in the same manner as in the first embodiment, and therefore the description thereof is omitted.

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

Then, as shown in (g) and (h) of FIG. 2, in the separation step, the support 1 is altered by irradiating the support 1 with light toward the separation layer 2 to change the quality of the support 1 Separated from the laminate 9. Further, thereafter, in the removing step, the adhesive layer 3 is removed using a hydrocarbon solvent in the same manner as in the first embodiment, whereby the sealing substrate 7 can be obtained ((i) in FIG. 2 ).

[Embodiment 3]
The following will describe another embodiment of the present invention. For convenience of explanation, members having the same functions as those described in Embodiments 1 and 2 will be designated by the same reference numerals, and the description thereof will be omitted. The method for manufacturing a laminated body and the method for manufacturing a sealing substrate according to Embodiment 3 include a separation layer forming step, a separation layer peripheral portion removing step, an adhesive layer forming step, a sealing substrate forming step, and an adhesive layer removing step. Carry out 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 therefore the description thereof is omitted.

[Separation layer peripheral edge removal step]
As shown in FIG. 3B, in the separation layer peripheral edge removing step, the separation layer 2 formed on the entire periphery of the peripheral edge 1b of the support 1 is removed by, for example, 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 a portion surrounded by the peripheral portion 1b where the separation layer 2 is removed. Details of the EBR process 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 entire periphery of the peripheral edge portion 1b from which the separation layer 2 has been removed. 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, its description is omitted.

[Sealing substrate forming process]
As shown in (d) to (g) of FIG. 3, in the sealing substrate forming step, the sealing substrate 7′ is formed on the adhesive layer 3. In the encapsulation substrate forming process of this embodiment, a rewiring layer forming process, a mounting process, a sealing process, and a thinning process are performed in this order.

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

Since the method of forming the redistribution layer 4 is the same as that of the first embodiment, its description is omitted.

As shown in (e) to (g) of FIG. 3, also in the third embodiment, the mounting step, the sealing step, and the thinning step are performed. 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, the adhesive layer 3 formed on the entire circumference of the peripheral edge portion 1b of the support 1 is removed by, for example, EBR treatment. The portion of the adhesive layer 3 formed on the entire circumference of the peripheral portion 1b of the support 1 bonds the support 1 and the sealing substrate 7′ without the separation layer 2, so that the portion 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 outside 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 always 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 (i) to (k) of FIG. 3, the sealing substrate 7′ can be manufactured by performing the separating step and the removing step as in the first embodiment.

(EBR processing)
In the (A) separation layer peripheral edge removing step, the EBR process for removing the separation layer 2 formed on the entire periphery of the peripheral portion 1b of the support 1, and the (B) adhesive layer removing step, the support The EBR treatment for removing the adhesive layer 3 formed on the entire circumference of the peripheral edge portion 1b of 1 is, for example, (i) a method of dissolving and removing with a solvent, (ii) physically using a cutter or a blade, etc. Examples include a method of cutting and removing, and a method of (iii) removing by ashing under atmospheric pressure. Among these, the 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 is not particularly limited as long as it can dissolve the separation layer 2 or the adhesive layer 3 to be removed, and a person skilled in the art can, depending on the composition to be removed, It can be appropriately selected. For example, a terpene solvent such as p-menthane and a condensed ring hydrocarbon such as tetrahydronaphthalene can be used for the adhesive layer 3. Further, for 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 tertiary aliphatic amine such as triethanolamine. At least one amine selected from the group consisting of a primary aliphatic amine, an alicyclic amine such as cyclohexylamine, an aromatic amine such as benzylamine, and a heterocyclic amine such as N-hydroxyethylpiperidine, or A solvent containing them can be used. As the solvent, organic solvents other than the terpene solvent among those listed in the above section (Additional solvent) can be preferably used.

Examples of the method of supplying the solvent include a method of supplying the solvent to the removal target by jetting 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 jetting the solvent, a method of supplying the solvent to the removal target while rotating the support 1 is preferable in order to uniformly supply the solvent. As a method of supplying the solvent while rotating the support 1, for example, a nozzle for ejecting the solvent is arranged immediately above the peripheral portion 1b of the support 1, and the solvent is supplied to the peripheral portion 1b of the support 1. A method of rotating the support 1 using a spinner while dropping it immediately to the outside can be mentioned. As a result, the solvent can be supplied to the immediate outer side 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 solvent supply time are the composition to be removed and the thickness to be removed. Although it may vary depending on the type of solvent used and the degree of removal, those skilled in the art can study and determine the optimum conditions without difficulty.

Further, it is preferable to dry the support 1 and the like after the removal of the object to be removed with the solvent. By passing through the drying step, it is possible to remove the unnecessary solvent and the solvent that has penetrated into the separation layer 2 or the adhesive layer 3 that is not the removal target portion.

Examples of the drying method include shake-off drying by rotating the support 1 using a spinner or the like, drying by air blow by spraying nitrogen gas or the like, drying by baking, and drying by reduced pressure. In addition, as a method for drying these, either one of the methods can be used alone, or any two or more methods can be used in combination.

[Embodiment 4]
The following will describe another embodiment of the present invention. For convenience of description, members having the same functions as the members described in the first to third embodiments will be designated by the same reference numerals, and the description thereof will be omitted. The method for manufacturing a laminate and the method for manufacturing a sealing substrate according to Embodiment 4 include a separation layer forming step, a separation layer peripheral edge removing step, an adhesive layer forming step, a sealing substrate forming step, and an adhesive layer removing step. Carry out in order.

[Separation layer forming step to adhesive layer forming step]
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, and therefore their explanations are omitted.

[Sealing substrate forming process]
In the sealing substrate forming step, the element 5 is placed on the adhesive layer 3 and sealed. That is, the sealing substrate 7′ is formed by the same process as the second embodiment. Then, as shown in FIG. 4A, the outer peripheral edge of the sealing substrate 7′ is removed by trimming processing. The trimming of the sealing substrate 7 may be carried out by grinding with a known means such as a grinder. Thereby, in the subsequent step, the amine treatment can be suitably performed on the laminate 9′ (FIG. 4).

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

Then, similarly to Embodiments 1 to 3, the sealing substrate 7'can be manufactured by removing the adhesive layer 3 with a hydrocarbon solvent.

[Another embodiment]
The laminated body manufacturing method and substrate processing method according to the present invention are not limited to the above-described respective embodiments (Embodiment 1, Embodiment 2, Embodiment 3, and Embodiment 4). For example, in the method for manufacturing a laminated body according to another embodiment, the sealing substrate in the laminated body formed by the method for manufacturing a laminated body according to each embodiment is separated via another adhesive layer and another separation layer. It is a method for producing a laminate to be laminated on the support. Thereby, the support on the adhesive layer side used to form the sealing substrate is separated, and the sealing substrate can be favorably processed in a state where the supporting substrate is supported by another support. it can.

Further, a method for producing 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, which is on the substrate, or An adhesive layer forming step of forming the adhesive layer by applying the adhesive composition according to an embodiment of the present application to at least one side of the support and heating it is included. Here, the substrate may be a flexible substrate such as silicon, ceramic, or polyimide resin, and may typically be a silicon interposer.

According to the above configuration, for example, the silicon interposer can be favorably processed on the support to form the through electrode. That is, by forming an adhesive layer using the adhesive composition according to one embodiment, it is possible to preferably form a laminated body even in the fan-in type semiconductor encapsulation technique.

The present invention is not limited to the above-described embodiments, but various modifications can be made within the scope of the claims, and 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 1-5 were prepared using only the base polymer as the resin component. Moreover, the adhesive composition of Examples 6-9 which used the base polymer and curable monomer as a resin component was prepared. In addition, the adhesive compositions of Comparative Examples 1 and 2 were prepared. After that, an adhesive layer was formed using the adhesive compositions of Examples 1 to 9 and Comparative Examples 1 and 2, and in each adhesive layer, the applicability evaluation to the sealing of the element by the compression mold, the insulating pattern forming process. The adaptability to

[Preparation of adhesive composition and formation of adhesive layer]
(Example 1)
First, as a base polymer, 100 parts by weight of acrylic resin II was dissolved in 400 parts by weight of decahydronaphthalene (main solvent). Then, 1 part by weight of IRGANOX 1010 (thermal polymerization inhibitor: manufactured by BASF) was added to 100 parts by weight of the resin component to prepare an adhesive composition of Example 1. IRGANOX 1010 was dissolved in butyl acetate (addition solvent) and added such that the addition amount of butyl acetate was 10 parts by weight with respect to 100 parts by weight of the main solvent.

Then, by a CVD method using C ₄ F ₈ as a reaction gas on a glass support (10 cm×10 cm, thickness 700 μm) under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W and a film formation temperature of 240° C. A fluorocarbon film (thickness 1 μm) as a separation layer was formed.

Then, the adhesive composition of Example 1 was applied onto the separation layer formed on the glass support by a spin coating method while rotating at 1500 rpm. 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 (film thickness 3 μm). The adhesive layer of Example 1 was used in the following evaluations 1 and 2, respectively.

(Examples 2 to 5)
As Examples 2 to 5, an acrylic resin having a composition different from that of Example 1 was used as a base polymer, and a polymerization inhibitor was blended to prepare adhesive compositions. Next, the adhesive layers of Examples 2 to 5 were formed using these adhesive compositions.

(Example 6)
As the adhesive composition of Example 6, 90 parts by weight of acrylic resin I as a base polymer, and 10 parts by weight of A-DCP (tricyclodecane dimethanol diacrylate: manufactured by Shin Nakamura Chemical Co., Ltd.) as a curable monomer. Was dissolved in 400 parts by weight of decahydronaphthalene. Next, perloyl TCP (thermal polymerization initiator: manufactured by NOF CORPORATION) was added to 100 parts by weight of the curable monomer in an amount of 2 parts by weight to prepare an adhesive composition. The perloyl TCP was dissolved in 40 parts by weight of butyl acetate (addition solvent) and added to the resin component.

(Examples 7 to 9)
As Examples 7 to 9, the base polymer, the curable monomer, and the polymerization initiator were blended in a composition and a composition ratio different from those in Example 6 to prepare adhesive compositions. Subsequently, the adhesive layers of Examples 7 to 9 were formed using these adhesive compositions.

(Comparative Examples 1 and 2)
The adhesive compositions of Comparative Examples 1 and 2 were prepared according to the procedure for preparing the adhesive composition of Example 1 or Example 6 except that a (meth)acrylate polymer having a low glass transition temperature was used. Then, each of the adhesive compositions of Comparative Examples 1 and 2 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 monomer units and curable monomers that compose the base polymers used in Examples 1 to 9 and Comparative Examples 1 and 2 are as shown below. The compositions of Examples 1 to 9 and Comparative Examples 1 and 2 are shown in Tables 3 and 5 below.

[Monomer unit constituting the base polymer]
-Adamantyl methacrylate (ADMA) represented by the following formula (9)

・以下の式（１０）で示されるステアリルメタクリレート（ＳＴＭＡ）

-Stearyl methacrylate (STMA) represented by the following formula (10)

・以下の式（１１）で示されるイソボルニルメタクリレート（ＩＢＸＭＡ）

-Isobornyl methacrylate (IBXMA) represented by the following formula (11)

The compositions, weight average molecular weights, and glass transition temperatures of the acrylic resins used in Examples and Comparative Examples were determined by dynamic mechanical analysis (DMA) as shown in Tables 1 and 2 below. Is.

In Table 2, “CMI” means cyclohexylmaleimide, and “MMA” means methyl methacrylate.

Moreover, the glass transition temperature of each acrylic resin shown in Table 1 and Table 2 was 5° C./minute under the condition of a frequency of 1 Hz using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). It was determined based on the change in viscoelasticity measured by increasing the temperature from 40° C. to 300° C. at the rate of temperature increase.

[Curable monomer]
Tricyclodecane dimethanol diacrylate represented by the following formula (12) (Shin-Nakamura Chemical Co., Ltd., "A-DCP (trade name)")

〔重合開始剤〕
熱重合開始剤として、パーロイルＴＣＰ、パークミルＤ、及びパーオクタＯ（いずれも日本油脂株式会社製）を用いた。

[Polymerization initiator]
As the thermal polymerization initiator, Perloyl TCP, Perkmill D, and Perocta O (all manufactured by NOF CORPORATION) were used.

[Evaluation 1: Evaluation of adaptability for sealing element by compression type]
The bare chip was placed at a predetermined position in the adhesive layer of Example 1, and the bare chip was sealed with a sealant. The degree of displacement of the bare chip at this time was evaluated as the adaptability for sealing (molding) by the compression mold.

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

Next, the adhesive layer of Example 1 in which the bare chip was arranged was heated at 200° C. for 1 hour in a nitrogen atmosphere.

Next, with the bare chip placed, the glass support having the adhesive layer of Example 1 formed thereon was placed on a plate heated to 50° C., and a sealing agent containing 12 g of an epoxy resin (softening temperature 100° C.). (Approx.) was applied, and under a reduced pressure condition lower than 10 Pa, a pressure of 1 ton was applied by a pressing plate heated to 130° C. using a sticking device and compressed for 5 minutes ((c) and (d in FIG. 2). ) Corresponds to the placement process). Thus, the bare chip arranged on the adhesive layer was sealed with the sealing material to obtain the stacked body of Example 1 in which the sealed bodies were stacked.

The laminated body of Example 1 was observed from the glass surface side using an optical microscope to evaluate the degree of positional displacement of the bare chip 5 that was attached. As shown in FIG. 5, the sum of the moving distances in the X direction and the Y direction was obtained from the position where each bare chip 5 arranged on the adhesive layer 3 was pasted, and the sum was calculated as the moving distance of each bare chip. Then, 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 for sealing by the compression mold is evaluated as “◯” without displacement when the moving distance of the bare chip 5 is 20 μm or less, and “×” with displacement when the moving distance of the bare chip 5 is larger than 20 μm. It was evaluated as.

Note that the adhesive layers of Examples 2 to 9 and Comparative Examples 1 and 2 were also subjected to applicability evaluation for sealing the element with the compression mold according to the procedure in the evaluation of the adhesive layer of Example 1.

Tables 3 and 5 below show the results of the applicability evaluation for sealing the element by the compression mold.

[Evaluation 2: Evaluation of adaptability to insulating pattern formation process]
With respect to the adhesive layers of Examples 1 to 9 and Comparative Examples 1 and 2 prepared according to the same procedure as the adhesive layer used in Evaluation 1, the adaptability evaluation (Evaluation 2) to the insulating pattern forming process was performed. In the applicability evaluation to the insulating pattern forming process, the chemical resistance to the resist solvent and the heat resistance to the heat treatment after the pattern formation were evaluated.

The applicability of the adhesive layers of Examples 6 to 9 and Comparative Examples 1 and 2 to the insulating pattern formation process was evaluated by heating each adhesive layer at 200° C. for 1 hour in a nitrogen atmosphere. I did.

(Evaluation of chemical resistance)
First, for evaluation of a positive resist, an 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, and the composition was heated at 110° C. for 4 minutes. A 5 μm dry film was formed by preheating under the conditions. Next, pattern exposure was performed on the film using a parallel light exposure device (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 made of a positive resist in a line pattern having a width of 100 μm.

For the evaluation of the negative type resist, BL301 (containing NMP, manufactured by Asahi Kasei Co., Ltd.), which is a negative type 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 using a parallel light exposure machine (ghi) manufactured by ORC, it is immersed in cyclohexanone at 23° C. for 5 minutes to form a photosensitive insulating film by a negative resist in a line pattern of 100 μm width. did.

The chemical resistance was evaluated by visually observing a change 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. The chemical resistance was evaluated as "○" when there was no change in weight and appearance, and "X" when there was a change in weight or appearance (floating line pattern or presence of cracks in the adhesive layer). It was judged.

Tables 3 and 5 below show the evaluation results of chemical resistance in the applicability evaluation to the insulating pattern forming process.

(Evaluation of heat resistance)
Next, as an evaluation of heat resistance, it was evaluated whether or not shrinkage (shrink) was generated in the line pattern formed in a width of 100 μm for each adhesive layer evaluated for chemical resistance. Regarding the evaluation of heat resistance, for the adhesive layer on which the line pattern was formed by the positive resist, the change of the line pattern after the heat treatment in a nitrogen atmosphere at 200° C. for 3 hours was evaluated, and the line pattern was formed by the negative resist. The formed adhesive layer was evaluated for change in line pattern after heat treatment at 230° C. for 4 hours in a nitrogen atmosphere. The heat resistance was evaluated by measuring the width of the 100 μm wide line pattern after the heat treatment using an optical microscope, and if the increase/decrease in width was less than 5 μm, the heat resistance was evaluated as “◯” and the increase/decrease in width was 5 μm. If it was larger, the heat resistance was evaluated as "x".

Tables 3 and 5 below show the evaluation results of heat resistance in the applicability evaluation to the insulating pattern forming process.

After the heat resistance was evaluated, bare chips were placed on each of the adhesive layers having line patterns formed on the adhesive layers of Examples 1 to 9, and the bare chips were coated with an epoxy resin under the same conditions as in Evaluation 1. By sealing with the sealing agent containing, the laminated body which laminated the sealing substrate 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 laminate formed in Evaluations 1 and 2 toward the separation. Then, the glass support was separated from each laminate to expose the adhesive layer. D-limonene was used as the cleaning liquid, and spray cleaning was performed for 10 minutes to clean the sealing substrate with the adhesive layer remaining. Detergency was evaluated by visually checking the presence or absence of residue in the adhesive layer on the sealing substrate, and when no residue was found, the detergency was evaluated as "○", and when many residues were found. The detergency was evaluated as "x".

Table 3 below shows the compositions of the adhesive compositions of Examples 1 to 9 and the evaluation results.

Table 4 below shows the evaluation results of the glass transition temperatures of the adhesive layers of Examples 6 to 9. The evaluation result of the glass transition temperature in the adhesive layer of Examples 6-9 containing a curable monomer is shown. The glass transition temperatures of the adhesive layers of Examples 6 to 9 were glass in acrylic resins I to VI after preheating at 140° C. for 5 minutes and heat treatment at 200° C. for 1 hour in a nitrogen atmosphere. It was measured under the same conditions as the measurement of the transition temperature.

Table 5 below shows the compositions of the adhesive compositions of Comparative Examples 1 and 2 and the evaluation results.

(Evaluation results)
As shown in Table 3, for the applicability evaluation to the sealing of the element by the compression mold, the adhesive layers of Examples 1 to 5 using the base polymer having a glass transition temperature of 190° C. or higher and the curable monomer were blended. By doing so, in any of the adhesive layers of Examples 6 to 9 which showed a glass transition temperature of 190° C. or higher, no displacement of the arranged bare chip was observed (◯). On the other hand, as shown in Table 5, in the adhesive layers of Comparative Examples 1 and 2, a displacement of the bare chip of 500 μm or more was recognized (x).

In Table 6 below, for the adhesive layers of Example 1 and Comparative Example 1, the applicability evaluation for sealing the element by the compression mold was performed by changing the heating temperature in the pressing press from 130°C to 150°C and 170°C. The results of the replacement are shown below.

As shown in Table 6, in Comparative Example 1, a large chip movement (225 μm) was observed, whereas in Example 1, even if the plate temperature at the time of sealing was 170° C., there was almost no displacement of the chip position. Not seen (≦20 μm). From these results, by using a base polymer having a Tg of 190° C. or higher, or by using a base polymer having a Tg of 140° C. or higher and a curable monomer together, it is possible to deform even if a force is applied in a high temperature environment. It was confirmed that it was possible to form an adhesive layer that could prevent

Further, as shown in Table 3, in chemical resistance in the applicability evaluation to the insulating pattern forming process, the adhesive layers of Examples 1 to 9 are PGMEA and TMAH as used for developing a positive resist, and It was confirmed that they have high chemical resistance to NMP as used in the development of negative resist. It was also confirmed that the adhesive layers of Examples 6 to 9 containing the curable monomer had high chemical resistance to cyclohexanone used for developing the negative resist. From this result, it was confirmed that the adhesive composition according to one embodiment can be applied to the insulating pattern forming process using a positive resist and a negative resist. On the other hand, as shown in Table 5, in the adhesive layers of Comparative Examples 1 and 2, when PGMEA, NMP and cyclohexanone were used as the resist solvent, the adhesive layers were dissolved and a line pattern could not be formed. It was (×).

In the evaluation of heat resistance, in the adhesive layers of Examples 1 to 9, shrinkage of the resist pattern formed on the adhesive layer was not substantially recognized under the heating condition of 200° C. for 4 hours (◯). Also, in the adhesive layers of Examples 3 to 9, shrinkage of the resist pattern was hardly recognized even under heating conditions of 230° C. for 4 hours (◯). In the adhesive layers of Comparative Examples 1 and 2, shrinkage of the resist pattern was recognized (x) under heating conditions of 230° C. for 4 hours, and in the adhesive layer of Comparative Example 2, heating conditions of 200° C. for 4 hours were used. Also in the sample, shrinkage of the resist pattern was observed (x).

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 were subjected to the same conditions as those in the heat resistance evaluation in Evaluation 2 (200). The temperature was increased and decreased, and the amount of change in the width of the line pattern was measured. The results are shown in Table 7 below.

As shown in Table 7, 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 before and after the heat treatment in the pattern formation by the resist. It was possible to confirm that the degree of was almost unchanged.

From the results of Evaluation 1 and Evaluation 2 described above, the adhesive layers of Examples 1 to 9 have higher heat resistance and higher chemical resistance as a whole, as compared with the adhesive layers of Comparative Examples 1 and 2. I was able to confirm that.

In addition to this, as shown in Table 3, the adhesive layers of Examples 1 to 9 could be suitably washed and removed by D-limonene in the evaluation of detergency (evaluation 3) (◯).

From the above results, by using a (meth)acrylate polymer having a Tg of 190° C. or higher, or by blending a curable monomer with a (meth)acrylate polymer having a Tg of 140° C. or higher, it is possible to adapt to the insulating pattern forming process. It has been confirmed that it is possible to obtain an adhesive composition that is capable of forming an adhesive layer that is highly adaptable to the insulating pattern forming process.

The present invention can be suitably used particularly in manufacturing a semiconductor device by a fan-out type technology.

1 Support 3 Adhesive Layer 4 Rewiring Layer 5 Bare Chip (Element, Sealing Body)
6 Sealing material (sealing body)
7, 7'sealing substrate 8, 8', 9, 9'laminate

Claims (15)

A substrate, an adhesive layer, and an adhesive composition for forming the adhesive layer in a laminate formed by laminating a support in this order,
The glass transition temperature of the adhesive layer is 190° C. or higher,
The adhesive composition contains, as a resin component, a (meth)acrylate polymer having an aliphatic polycyclic group,
The (meth)acrylate polymer is characterized in that the content of the monomer unit having an aliphatic polycyclic group is in the range of 60% by weight or more and 100% by weight or less. The adhesive composition according to claim 1, further comprising a polyfunctional curable monomer as a resin component. The adhesive composition according to claim 1 or 2, wherein the glass transition temperature of the (meth)acrylate polymer having an aliphatic polycyclic group is 190°C or higher. The adhesive composition according to claim 2, wherein the (meth)acrylate polymer having an aliphatic polycyclic group has a glass transition temperature of 140°C or higher. The adhesive composition according to any one of claims 2 to 4, wherein the polyfunctional curable monomer has an aliphatic polycyclic group. Content of the said polyfunctional curable monomer in the said resin component is in the range of 1 to 30 weight% inclusive, Adhesion in any one of Claims 2-5 characterized by the above-mentioned. Agent composition. The adhesive composition according to any one of claims 1 to 6, wherein the (meth)acrylate polymer having an aliphatic polycyclic group has a weight average molecular weight of 90,000 or more. The (meth)acrylate polymer having an aliphatic polycyclic group is selected from the group consisting of a monomer unit having an aliphatic polycyclic group, a monomer unit having an alkyl group, and a monomer unit having an aromatic group. The adhesive composition according to any one of claims 1 to 7, which is a copolymer with at least one monomer unit. 9. The adhesive composition according to claim 1, wherein the aliphatic polycyclic group has at least one structure selected from tricycloalkane structure and tetracycloalkane structure. .. An adhesive film comprising an adhesive layer comprising the adhesive composition according to any one of claims 1 to 9 formed on the film. A method for producing a laminate, comprising: a substrate, an adhesive layer, and a support, which are laminated in this order,
An adhesive layer is formed by applying the adhesive composition according to any one of claims 1 to 8 on at least one of the substrate and the support and heating the adhesive composition to form the adhesive layer. A method for producing a laminate, which comprises the steps. The substrate is a sealing body including a sealing body formed by sealing an element with a sealing material, and a rewiring layer that is provided on one flat surface portion of the sealing body and forms a wiring connected to the element. It is a stop substrate,
On the support, the adhesive composition is applied, and the adhesive layer forming step of forming the adhesive layer by heating,
An arrangement step of arranging the element on the adhesive layer,
The manufacturing method of the laminated body of Claim 11 including the sealing process of sealing the said element with a sealing material after the said arrangement|positioning process. The substrate is a sealing substrate including a sealing body obtained by sealing an element with a sealing material, and a rewiring layer provided on one flat surface portion of the sealing body and in which the element is arranged. ,
On the support, the adhesive composition is applied, and the adhesive layer forming step of forming the adhesive layer by heating,
The method for producing a laminate according to claim 11, further comprising a rewiring layer forming step of forming the rewiring layer on the adhesive layer. The support is a support made of a material that transmits light,
14. The method according to claim 11, further comprising, before the adhesive layer forming step, a separating layer forming step of forming a separating layer which is deteriorated by irradiating light on the support. The method for producing a laminate according to item 1. A method for manufacturing the laminate according to claim 14;
Through the support, the separation layer is changed in quality by irradiating with light, and a separation step of separating the substrate from the laminate,
After the separating step, a removing step of removing the adhesive layer remaining on the substrate separated from the laminated body with a cleaning liquid is included.

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