JP6722001B2 - Adhesive composition, laminate, and method for producing laminate - Google Patents

Description

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

A WLP (Wafer Level Package) or the like is known as a semiconductor package (semiconductor device) including a semiconductor element (electronic component). For semiconductor packages such as WLP and PLP, the fan-in type technology such as fan-in type WLP (Fan-in Wafer Level Package) that rearranges the terminals at the end of the bare chip in the chip area and the outside of 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 has been applied to a fan-out type PLP (Fan-out Panel Level Package) in which a semiconductor element is arranged on a panel and packaged, 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 optical emulsion containing an aqueous emulsion containing polymer particles made of an acrylic copolymer, organic fine particles, a curing agent capable of curing the acrylic copolymer, and a quaternary ammonium compound. A diffusive pressure sensitive adhesive composition is described.

Patent Document 2 describes a curable composition containing a styrene-olefin block copolymer, a (meth)acrylic acid ester, and a solvent as essential components.

Patent Document 3 discloses a resin composition containing a chain-polymerizable monomer, a cross-linking agent that cross-links in a sequential reaction, and a cross-linkable polymer having a cross-linkable group that reacts with the cross-linking agent. The support has a crosslinked relief-forming layer crosslinked by polymerization and a sequential crosslinking reaction, and the storage elastic modulus E′ (MPa) of the crosslinked relief-forming layer at a frequency of 100 Hz at 25° C. is 1≦E′≦30. The laser engraving type flexographic printing plate precursor is described which satisfies the relationship (1) and the maximum elongation L (%) at 25° C. at tensile break of 30≦L≦300.

Patent Document 4 includes a base material to be ground, a bonding layer in contact with the base material to be ground, a photothermal conversion layer containing a light absorber and a thermally decomposable resin, and a light transmissive support, However, the photothermal conversion layer is decomposed when irradiated with radiant energy after grinding the surface of the base material to be ground on the side opposite to the bonding layer, and the base material after grinding and the light transmissivity. A laminate is described which is separate from the support.

Patent Document 5 describes an adhesive composition comprising a polymer having a cycloolefin structure and a (meth)acrylate monomer compatible with the polymer.

JP, 2010-053347, A (published on March 11, 2010) JP, 2010-077384, A (published on April 8, 2010) Japanese Unexamined Patent Publication No. 2011-206931 (Published October 20, 2011) Japanese Patent Laid-Open No. 2004-64040 (Published February 26, 2004) JP-A-2014-105316 (Published June 9, 2014)

However, in Patent Documents 1 to 5, the fan-out type technology has high chemical resistance as required when manufacturing a sealed body, and maintains high viscoelasticity when heated to a high temperature. Nothing is disclosed about an adhesive composition capable of forming a possible adhesive layer.

In the fan-out type technology, the present inventors have a high chemical resistance by using a curable adhesive composition containing a block copolymer and a polymerizable monomer, and have high viscoelasticity when heated to a high temperature. The present invention has been completed by finding that an adhesive layer capable of maintaining the above can be formed, and that the adhesive layer is useful for forming a sealed body.

The present invention has been made in view of the above-mentioned problems, and an object thereof is an adhesive composition used in a laminate for forming a sealed body by a fan-out type technique, which has a high chemical content. An object of the present invention is to provide an adhesive composition having resistance and capable of forming an adhesive layer capable of maintaining high viscoelasticity at high temperatures, and a related technique thereof.

In order to solve the above problems, the adhesive composition according to the present invention provides a wiring layer on which an element is mounted, the element, and a sealing body that includes a sealing material that seals the element. The adhesive composition for forming the adhesive layer in a laminate obtained by laminating an adhesive layer on a support supporting the sealing body, wherein the adhesive composition is a block It is characterized in that it contains a polymer, a polymerizable monomer, and a polymerization initiator.

Further, the laminated body according to the present invention supports a sealing body that includes a wiring layer on which an element is mounted, the element, and a sealing material that seals the element, and that supports the sealing body. A laminate formed by laminating an adhesive layer on a body, wherein the adhesive layer comprises a block copolymer, a polymer of a polymerizable monomer, and a polymerization initiator. There is.

ADVANTAGE OF THE INVENTION According to this invention, it is an adhesive composition used for the laminated body for forming a sealing body by a fan-out type|mold technique, It has high chemical resistance and can maintain high viscoelasticity at high temperature. It is possible to provide an adhesive composition capable of forming an adhesive layer 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. It is a figure explaining the manufacturing method of the laminated body which concerns on Embodiment 2 of this invention. It is a figure explaining the manufacturing method of the laminated body which concerns on Embodiment 3 of this invention. It is a figure explaining the manufacturing method of the laminated body which concerns on Embodiment 4 of this invention.

<Adhesive composition>
The adhesive composition according to the present invention supports a sealing body that includes a wiring layer on which an element is mounted, the element, and a sealing material that seals the element, and supports the sealing body. It is an adhesive composition for forming the above-mentioned adhesive layer in a layered product laminated on a body via an adhesive layer. In other words, an adhesive layer for forming a sealing body including a wiring layer on which the element is mounted, the element, and a sealing material for sealing the element on the support is provided on the support. It is an adhesive composition for forming.

The adhesive composition contains a block copolymer and a polymerizable monomer as a resin composition for forming an adhesive layer, a polymerization initiator for polymerizing the polymerizable monomer, and coating workability of the resin composition. And a diluting solvent for adjusting The adhesive composition more preferably employs a resin composition composed of a block copolymer and a polymerizable monomer as the resin composition for forming the adhesive layer.

The adhesive composition is heated or placed in a reduced pressure environment or the like to remove the diluting solvent, and the polymerizable monomer is polymerized with a polymerization initiator in the block copolymer to form an adhesive layer. The adhesive layer has high chemical resistance because it contains the block copolymer, and when it is heated to high temperature, it has high viscoelasticity, that is, high dynamic complex elasticity, by polymerizing the polymerizable monomer. The rate can be maintained. Therefore, an adhesive layer that can be suitably used in a fan-out type technology that requires forming a wiring layer using various resist solvents and sealing an element with a sealing material at high temperature is formed. be able to.

[Block copolymer]
The block copolymer is a polymer in which two or more kinds of block sites in which monomer units are continuously bonded are bonded, and is typically a thermoplastic elastomer having a polymer block. By containing the block copolymer, it is possible to form an adhesive layer having high cleanability and high chemical resistance.

The block copolymer is preferably a diblock copolymer or a triblock copolymer, more preferably a triblock copolymer. Moreover, you may use combining a diblock copolymer and a triblock copolymer.

In addition, the block copolymer may have a terminal modified with a functional group by using a modifier. Here, as the functional group, for example, amino group, acid anhydride group (preferably maleic anhydride group), imide group, urethane group, epoxy group, imino group, hydroxyl group, carboxyl group, silanol group, and alkoxysilane group (The alkoxy group preferably has 1 to 6 carbon atoms). As described above, the block copolymer modified with the modifier is an elastomer and has a functional group that brings polarity. Therefore, the flexibility and adhesiveness of the adhesive layer can be improved.

The block copolymer preferably contains a styrene block, and more preferably a triblock copolymer in which both ends of the main chain are styrene blocks. By using a triblock copolymer having styrene blocks at both ends, the thermal stability of the adhesive layer can be increased.

Examples of the block copolymer containing a styrene block include a styrene-olefin block copolymer.

Examples of the styrene-olefin block copolymer include polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene. -Butadiene-butylene-styrene block copolymer (SBBS), and hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) ) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene block reactive cross-linking styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (stock) Kuraray Co., Ltd.), a styrene block is a reaction cross-linking type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (made by Kuraray Co., Ltd.) having a reactive polystyrene-based hard block), and polystyrene-poly(ethylene-). Examples thereof include ethylene/propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification).

Further, the block copolymer is preferably a hydrogenated product, and more specifically, a hydrogenated product of a block copolymer of a styrene block and a conjugated diene block is more preferable. By using the hydrogenated product of the block copolymer, stability against heat can be improved, and deterioration such as decomposition or polymerization can be made difficult to occur. Furthermore, high compatibility with a hydrocarbon solvent can be brought about, and low compatibility with a resist solvent, that is, high resistance against a resist solvent can be brought about.

Examples of commercially available products that can be used as the block copolymer include "Septon (trade name)" manufactured by Kuraray Co., Ltd., "High Blur (trade name)" manufactured by Kuraray Co., Ltd. and "Tuftec (trade name)" manufactured by Asahi Kasei Corporation. And "Dynaron (trade name)" manufactured by JSR Corporation.

The content of the styrene block in the block copolymer is preferably 10% by weight or more and 65% by weight or less, and more preferably 13% by weight or more and 45% by weight or less. The block copolymer tends to maintain a high dynamic complex elastic modulus when heated to a high temperature, as the content of the styrene block increases. Further, the smaller the content of the styrene block, the higher the compatibility with the hydrocarbon solvent tends to be obtained.

The weight average molecular weight of the block copolymer is preferably 50,000 or more and 150,000 or less, more preferably 60,000 or more and 120,000 or less. A block copolymer having a higher weight average molecular weight tends to be able to maintain a high dynamic complex elastic modulus when heated to a high temperature. Further, the smaller the weight average molecular weight, the higher the compatibility with a hydrocarbon solvent, for example.

The block copolymer is adjusted so that the content of the styrene block is 10% by weight or more and 65% by weight or less, and the weight average molecular weight is 50,000 or more and 150,000 or less. Is most preferred. The adhesive composition may use one block copolymer having a styrene block content within the above range and a weight average molecular weight within the above range, and a plurality of types of block copolymers may be used. By mixing, the styrene block content may be adjusted to fall within the above range, and the weight average molecular weight may be adjusted to fall within the above range.

For example, Septon (trade name) Septon 4033 manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon (trade name) Septon 2063 having a styrene unit content of 13% by weight are used in a weight ratio of 1 When mixed in a ratio of 1, the styrene content with respect to the entire block copolymer contained in the adhesive is 21 to 22% by weight, and thus 10% by weight or more. Further, for example, when a styrene unit having a styrene unit content of 10% by weight and a styrene unit having a styrene unit content of 60% by weight are mixed at a weight ratio of 1:1, the content is 35% by weight, which is within the above range. The present invention may have such a form. Most preferably, the plurality of types of elastomers contained in the adhesive composition all contain a styrene block within the above range and have a weight average molecular weight within the above range.

By adjusting the content of the styrene block in the block copolymer within the above range and adjusting the weight average molecular weight within the above range, the adhesive layer is swollen by the hydrocarbon solvent and partially dissolved. And can be easily removed. Further, it is possible to obtain high resistance to a resist solvent (eg, propylene glycol monomethyl ether acetate (PGMEA)), an acid (hydrofluoric acid, etc.) and alkali tetramethylammonium hydroxide (TMAH) used in resist lithography. .. Further, by adjusting the content of the styrene block in the block copolymer within the above range and adjusting the weight average molecular weight within the above range, the heat resistance of the block copolymer itself which is the base resin By improving the viscoelasticity at high temperature, the amount of the polymerizable monomer to be described later can be reduced.

The amount of the block copolymer contained in the adhesive composition is preferably in the range of 50% by weight or more and 99% by weight or less, based on 100% by weight of the total amount of the block copolymer and the polymerizable monomer. , 60 wt% or more and 95 wt% or less is more preferable, and 80 wt% or more and 95 wt% or less is most preferable. When the amount of the block copolymer contained in the adhesive composition is in the range of 50% by weight or more and 99% by weight or less, the adhesive layer has high compatibility with the hydrocarbon solvent derived from the block copolymerization. Can be maintained, and the removal of the adhesive layer by washing can be facilitated.

[Polymerizable monomer]
The adhesive composition contains a polymerizable monomer. The polymerizable monomer is preferably a monomer that is polymerized by radical polymerization, and typically, a polyfunctional (meth)acrylic acid ester can be mentioned.

The polyfunctional (meth)acrylic acid ester may be a bifunctional or higher functional (meth)acrylic acid ester, or a trifunctional or higher functional polyfunctional (meth)acrylic acid ester. By using a bifunctional or trifunctional or higher functional (meth)acrylic acid ester, it is possible to preferably form a three-dimensional network structure of the polymer of the (meth)acrylic acid ester in the block copolymer of the adhesive layer. Therefore, the chemical resistance of the adhesive layer can be increased, and the viscoelasticity of the adhesive layer when heated to a high temperature, that is, the dynamic complex elastic modulus can be increased.

As the bifunctional (meth)acrylic acid ester, a polyethylene glycol diacrylate having a weight average molecular weight of 200 to 1000 in the main chain, a polypropylene glycol diacrylate having a weight average molecular weight of 50 to 700 in the polypropylene glycol main chain, Polyether di(meth)acrylate such as polyethylene glycol dimethacrylate having a degree of polymerization of oxyethylene structural unit of 1 or more and 23 or less can be mentioned, and ethoxy having a degree of polymerization of oxyethylene structural unit of 3 or more and 30 or less. Bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate having a degree of polymerization of oxyethylene constitutional units of 2.3 or more and 30 or less, propoxylated bisphenol A diacrylate, bisphenol type diethoxy propoxylated bisphenol A diacrylate, etc. (Meth)acrylate can be mentioned. Further, ethoxylated polypropylene glycol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2,2 bis[4-(methacryloxyethoxy)phenyl]propane, 9,9-bis[4-(2-acryloyloxy) Examples include di(meth)acrylates having an ether skeleton such as ethoxy)phenyl]fluorene, glycerin dimethacrylate, polytetramethylene glycol diacrylate, and tricyclodecane dimethanol di(meth)acrylate, 1,10-decanediol. It has a carbon skeleton such as di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, or a cyclic hydrocarbon skeleton. Di(meth)acrylate may be mentioned.

From the viewpoint of compatibility with the block copolymer, among the above-mentioned polyfunctional (meth)acrylic acid esters, an ester having a hydrocarbon skeleton is preferable, and an ester having a cyclic hydrocarbon skeleton is more preferable. ..

Examples of commercially available products that can be used as the bifunctional (meth)acrylic acid ester include "701A (trade name)", "A-200 (trade name)", and "A-400 (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd. Name)”, “A-600 (trade name)”, “A-1000 (trade name)”, “A-B1206PE (trade name)”, “ABE-300 (trade name)”, “A-BPE-10”. (Trade name)", "A-BPE-20 (trade name)", "A-BPE-30 (trade name)", "A-BPE-4 (trade name)", "A-BPEF (trade name)" , "A-BPP-3 (trade name)", "A-DCP (trade name)", "A-DOD-N (trade name)", "A-HD-N (trade name)", "A" -NOD-N (product name)", "APG-100 (product name)", "APG-200 (product name)", "APG-400 (product name)", "APG-700 (product name)", "A-PTMG-65 (product name)", "1G (product name)", "2G (product name)", "3G (product name)", "4G (product name)", "9G (product name) , "14G (trade name)", "23G (trade name)", "BPE-80N (trade name)", "BPE-100 (trade name)", "BPE-200 (trade name)", "BPE" -500 (trade name), BPE-900 (trade name), BPE-1300N (trade name), DCP (trade name), DOD-N (trade name), HD-N (Product Name), "NOD-N (Product Name)", "NPG-N (Product Name)", "1206PE (Product Name)", "701 (Product Name)", "9PG (Product Name)", etc. Are listed.

Examples of commercially available products that can be used as the polyfunctional (meth)acrylic acid ester include "A-9300 (trade name)", "A-9300-1CL (trade name)" and "A" manufactured by Shin-Nakamura Chemical Co., Ltd. -GLY-9E (trade name)", "A-GLY-20E (trade name)", "A-TMM-3 (trade name)", "A-TMM-3-L (trade name)", "A -TMM-3LM-N (trade name)", "A-TMPT (trade name)", "AD-TMP (trade name)", "ATM-35E (trade name)", "A-TMMT (trade name)" , “A-9550 (trade name)”, “A-DPH (trade name)”, “TMPT (trade name)” and the like.

The amount of the polymerizable monomer contained in the adhesive composition is, for example, preferably in the range of 1% by weight or more and 50% by weight or less, with the total amount of the block copolymer and the polymerizable monomer being 100% by weight, It is more preferably within the range of 1% by weight or more and less than 20% by weight. The larger the amount of the polymerizable monomer, the higher the dynamic complex elastic modulus when the adhesive layer is heated to a high temperature. In addition, the chemical resistance of the adhesive layer can be increased, and in particular, the resistance to resist solvents such as cyclohexanone, cyclopentanone, and N-methyl-2-pyrrolidone (NMP) as well as PGMEA can be increased. In addition, as the amount of the polymerizable monomer decreases, the adhesive layer can maintain high detergency when a hydrocarbon solvent derived from the block copolymer is used. Therefore, the adhesive composition increases the dynamic complex elastic modulus of the block copolymer itself by adjusting the content and the weight average molecular weight of the styrene block in the block copolymer, and a relatively small amount of the polymerizable monomer is added. It is preferable to increase the dynamic complex elastic modulus by blending. In particular, maintaining a high viscoelasticity by blending the polymerizable monomer in the range of 1% by weight or more and less than 20% by weight, with the total amount of the block copolymer and the polymerizable monomer being 100% by weight. It is possible to solve both of the problems that are easily removed with a solvent and that may have a trade-off relationship at first glance.

The polyfunctional (meth)acrylic acid ester is a monofunctional (meth)acrylic acid ester, as well as, for example, urethane (meth)acrylate, epoxy (meth), to the extent that the viscoelasticity when heated to a high temperature is not deteriorated. A polymerizable monomer such as acrylate, styrene, divinylbenzene, and vinyl acetate may be used in combination.

(Complex elastic modulus of adhesive layer)
The complex elastic modulus of the adhesive layer formed by the adhesive composition when heated to a high temperature is increased by the block copolymer and the polymer of the polymerizable monomer. For this reason, it is possible to prevent the adhesive layer from being distorted in the environment of high temperature (100° C. or higher and 400° C. or lower) and high pressure (10 kgf or higher) when the sealed body is formed on the adhesive layer. Here, the complex elastic modulus (E*) of the adhesive layer formed by the adhesive composition varies depending on the temperature condition to which it is applied, but is, for example, preferably 1000 Pa or more, more preferably 10000 Pa or more. .. If the dynamic complex elastic modulus (E*) of the adhesive layer is 10,000 Pa or more at the temperature applied when forming the sealing body, the adhesive layer is distorted when pressure is applied in the high temperature process. This can be prevented more favorably. For the dynamic complex elastic modulus (E*), a 6-inch Si wafer is spin-coated with an adhesive composition to form a film (adhesive layer) having a predetermined thickness. A sample may be prepared by peeling the film and cutting it into a predetermined size. In addition, while increasing the temperature of the sample to a temperature equal to or higher than the temperature assumed when forming the sealed body at a temperature increase rate of 5° C./min under the condition of a frequency of 1 Hz, the dynamic complex elastic modulus (E *) should be measured. For example, if the temperature assumed when forming the encapsulant is about 100 to 200° C., the dynamic complex elastic modulus (E*) is measured while increasing the temperature from 50° C. to 250° C., for example. Good.

(Diluting solvent)
The diluent solvent contained in the adhesive composition may be one that can dissolve the block copolymer and the polymerizable monomer, for example, a nonpolar hydrocarbon solvent, a polar and nonpolar petroleum solvent. Etc. can be used.

Preferably, the diluting solvent may include condensed polycyclic hydrocarbon. When the solvent contains the condensed polycyclic hydrocarbon, it is possible to avoid clouding that may occur when the adhesive composition is stored in a liquid form (especially at low temperature), and it is possible to improve product stability. ..

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 and tridecane, branched hydrocarbons having 3 to 15 carbon atoms; p-menthane, o-menthane, m -Saturated aliphatic hydrocarbons such as menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, tsujan, karan, longifolene, α-terpinene, β-terpinene, γ-terpinene, α -Pinene, β-pinene, α-tsujone, β-tsujone and the like.

Further, examples of the petroleum solvent include cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene and the like.

The condensed polycyclic hydrocarbon is a condensed ring hydrocarbon formed by two or more monocycles sharing only one side of each ring, and is a hydrocarbon formed by condensing two monocycles. Preference is given to using hydrogen.

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.

Further, when the diluent solvent contains the condensed polycyclic hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon, for example, other components such as saturated aliphatic hydrocarbons. It may be contained. In this case, the content of the condensed polycyclic hydrocarbon is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, when the total amount of the hydrocarbon solvent is 100 parts by weight. When the content of the condensed polycyclic hydrocarbon is 40 parts by weight or more, high solubility in the resin can be exhibited. When the hydrocarbon solvent contains the condensed polycyclic hydrocarbon and the saturated aliphatic hydrocarbon, 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 by using the adhesive composition, for example, the total amount of the adhesive composition. When the 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 diluting solvent is within the above range, viscosity adjustment becomes easy.

[Polymerization initiator]
The polymerization initiator is not particularly limited as long as it can polymerize the above-mentioned polymerizable monomer, and is preferably a thermal polymerization initiator or a photopolymerization initiator, and more preferably a thermal polymerization initiator. ..

(Thermal polymerization initiator)
Examples of the thermal polymerization initiator include peroxides and azo polymerization initiators. These thermal polymerization initiators polymerize the polymerizable monomer by radicals generated by heating.

Examples of peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, peroxycarbonates and peroxyketals. Specifically, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-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 performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, per-4-methoxyacetic acid tert-butyl and tert-butyl perN-(3-toluyl)carbamate, dicumyl-peroxide, tert-butyl-peroxy-2-ethylhexyl-monocarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)cyclohexane and the like can be mentioned.

Examples of commercially available peroxides include trade names “Park Mill (registered trademark)”, trade names “Perbutyl (registered trademark)”, trade names “Perocta (registered trademark)” and “Perloyl” manufactured by NOF CORPORATION. (Registered trademark)” and “Perhexa (registered trademark)”.

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) and poly(tetraethylene glycol-2,2'-azobisisobuty) Rate) and the like.

The blending amount of the thermal polymerization initiator is preferably 0.1 part by weight or more and 20 parts by weight or less, and more preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polymerizable monomer. More preferable. Thereby, the polymerizable monomer contained in the adhesive layer can be suitably polymerized. The thermal polymerization initiator may be added to the adhesive composition by a known method immediately before using the adhesive composition. The thermal polymerization initiator may be added to the adhesive composition after being diluted with an additive solvent described below.

The one-minute half-life temperature of the thermal polymerization initiator is preferably 90° C. or higher and 200° C. or lower, and more preferably 120° C. or higher and 180° C. or lower.

Further, the one-hour half-life temperature of the thermal polymerization initiator is preferably 50° C. or higher and 140° C. or lower, and more preferably 80° C. or higher and 140° C. or lower.

The 1-minute half-life temperature of the thermal polymerization initiator is 90° C. or higher and 200° C. or lower, and the 1-hour half-life temperature is 50° C. or higher and 140° C. or lower. It is possible to lengthen the time required for the polymerizable monomer to polymerize and gel. This can prolong the workable time when the adhesive composition is applied on the support. Further, the one-minute half-life temperature of the thermal polymerization initiator is 90° C. or more and 200° C. or less and the one-hour half-life temperature is 50° C. or more and 140° C. or less, so that the adhesive composition is formed on the support. When the diluent solvent is removed by coating and heating, radicals can be simultaneously generated to preliminarily initiate the polymerization of the polymerizable monomer. From the viewpoint that the workable time can be lengthened, it is preferable that the 1-minute half-life temperature and the 1-hour half-life temperature of the thermal polymerization initiator are higher. From the viewpoint of prompt gelation, it is preferable that the 1-minute half-life temperature and the 1-hour half-life temperature of the thermal polymerization initiator are lower.

The theoretical active oxygen amount of the thermal polymerization initiator is preferably 3.0% or more and 13.0% or less, and the compounding amount of the thermal polymerization initiator may be appropriately adjusted according to the theoretical active oxygen amount. ..

(Photopolymerization initiator)
The adhesive composition is capable of forming an adhesive layer having high chemical resistance and high heat resistance and further having high cleanability by polymerizing a polymerizable monomer with a photopolymerization initiator. .. In the case of using a photopolymerization initiator as the polymerization initiator, if the adhesive composition is packaged so that the light-shielded state can be maintained, the adhesive composition is mixed with the photopolymerization initiator. Can be commercialized.

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-mercaptobenzimidazole, 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 compounding amount of the photopolymerization initiator is preferably 0.1 part by weight or more and 20 parts by weight or less, and more preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polymerizable monomer. More preferable.

(Additional solvent)
It is preferable that the thermal polymerization initiator and the photopolymerization initiator are dissolved in an additive solvent and mixed into the adhesive composition. The addition solvent is not particularly limited, but an organic solvent capable of dissolving 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, a terpene solvent having an oxygen atom as a polar group, 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 , 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 types of the thermal polymerization initiator and the photopolymerization initiator, and for example, the total of the diluent solvent (main solvent) that dissolves the resin component and the added solvent is 100. The content of the additive solvent is preferably 1 part by weight or more and 50 parts by weight or less, and more preferably 1 part by weight or more and 30 parts by weight or less, when the amount is expressed as parts by weight. When the content of the added solvent is within the above range, the thermal polymerization initiator and the photopolymerization initiator can be sufficiently dissolved.

<Laminate>
A laminated body according to an embodiment of the present invention supports a sealing body that includes a wiring layer on which an element is mounted, the element, and a sealing material that seals the element, and supports the sealing body. Which is a laminate formed by laminating an adhesive layer on a support, wherein the adhesive layer comprises a block copolymer, a polymer of a polymerizable monomer, and a polymerization initiator. Further, a separation layer is provided between the support and the adhesive layer.

In the laminate according to the embodiment of the present invention, an adhesive layer is formed using the adhesive composition according to the embodiment of the present invention. Therefore, the wiring layer can be preferably formed on the adhesive layer formed on the support, and the element can be preferably sealed. Therefore, a laminated body in which an adhesive layer is formed using the adhesive composition according to one embodiment of the present invention is also within the scope of the present invention.

(Sealing body)
The sealing body includes a wiring layer on which the element is mounted, the element, and a sealing material that seals the element. The sealing body preferably includes a plurality of elements, and a plurality of electronic components can be obtained by dicing such a sealing body.

(Wiring layer)
The wiring 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 wiring layer includes a dielectric (eg, silicon oxide (SiOx), a photosensitive resin such as photosensitive epoxy, etc.) and a conductor (eg, aluminum, copper, titanium, nickel, gold, silver, etc.). The wiring may be formed of a metal or an alloy such as a silver-tin alloy), but is not limited thereto.

(element)
The device is a semiconductor device or other device 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 body is a semiconductor device.

(Sealing material)
As the sealing material, for example, a sealing material containing an epoxy resin or the like 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 wiring layer.

[Support]
The support may have a strength necessary to prevent damage or deformation of each component of the sealing body when forming the sealing body. In addition, 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. As the shape of the support, for example, a plate-shaped circular support can be used, but is not limited thereto.

[Adhesive layer]
The adhesive layer comprises a block copolymer, a polymer of a polymerizable monomer, and a polymerization initiator, and is used for fixing the sealing body on the support and for protecting the separation layer. To be

Here, the adhesive composition for forming the adhesive layer is as described above, and since the block polymer, the polymerizable monomer, and the polymerization initiator are the same as those described above, the description thereof will be omitted.

The polymer of the polymerizable monomer is preferably a polyfunctional (meth)acrylic acid ester polymer. Since the polyfunctional (meth)acrylic acid ester is the same as that described above, the description is omitted.

The thickness of the adhesive layer may be appropriately set depending on the types of the support and the sealing body, the treatment to be performed when forming the sealing body, 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 body 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 body by irradiating the separation layer with light through the support to change the quality of the separation layer.

In the present specification, the term “deteriorates” the separation layer means a phenomenon in which the separation layer can be destroyed by receiving a small external force, or a state in which the adhesion between the separation layer and a layer in contact with the separation layer is reduced. To do. As a result of alteration of the separation layer caused by absorption of 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 energy of absorbed light, changes in 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 laminated 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) equipped with suction means. By separating the support plate and the substrate, or by gripping the chamfered portion at the peripheral edge of the support plate with 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. In addition, for example, the support plate may be peeled from the substrate in the laminate by using a support separation device including 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 depending on the size of the laminated body and the like and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, a force of about 0.1 to 5 kgf is applied. By adding, the substrate and the support plate can be suitably separated.

The thickness of the separation layer is more preferably, for example, 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. 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 may be used. It may be added to form a separation layer. Further, it is preferable that the surface of the separation layer 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. Since the separation layer is made of fluorocarbon, 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), the separation layer is broken, and the support and the sealing body 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, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, a solid-state laser such as an LD laser or a fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that the fluorocarbon can absorb. , 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 for example, a wavelength in the range of 600 nm or less can be used.

(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 altered by being irradiated with light. The alteration of the polymer is caused by 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 broken, and the support and the sealing body 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:

(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, for example, the polymer contains 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.

(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). And (f) is one of the formulas shown in the above “Chemical Formula 1” or does not exist, and 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, and when Z is —SO ₂ — includes 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 when Z is —SO—, examples thereof include 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 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. If 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 body, and the irradiation time of light 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 above 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), or 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 its 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 broken, and the support and the sealing body 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 a range that the inorganic material used for the separation layer absorbs, the 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. A liquid laser such as CO ₂ laser, excimer laser, Ar laser, gas laser such as He—Ne laser, semiconductor laser, laser light such as free electron laser, or non-laser light may be used as appropriate.

The separation layer made of an inorganic material can be formed on the 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 the adhesive may be attached to the support.

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

(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 broken, and the support and the sealing body 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), alkyne (mono-substituted, di-substituted), monocyclic aromatic (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 compound, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or 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 the 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 by selecting the type. Specifically, the wavelength of infrared rays that can be absorbed by the above 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 above-mentioned 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, “Spectral Identification Method of Organic Compounds (Fifth Edition)-MS, IR, NMR, UV Combination-” (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 structure, 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 body, 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.

(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 the compound having a siloxane skeleton, a t-butylstyrene (TBST)-dimethylsiloxane copolymer which is a copolymer of the repeating unit represented by the 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 further preferable.

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. ..

(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 in 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.

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-propoxy titanium, tetra-n-butoxy titanium, tetrakis(2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. Alkoxy titanium such as; (ii) di-i-propoxy bis(acetylacetonato) titanium, and chelating titanium such as propanedioxytitanium bis(ethylacetoacetate); (iii) i-C ₃ H ₇ O-[- _{Ti (O-i-C 3} H 7) 2 -O-] n -i-C 3 H 7, 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)tributoxytitanium and the like acylate titanium; (v) di-n-butoxy.bis(triethanolaminato)titanium and the like 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 broken, and the support and the sealing body 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 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, as long as 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).

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 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 the chemical formula (8), p is preferably an integer of 1 or more and 100 or less, and more preferably an integer of 1 or more and 50 or less. 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. When R is a cyclic alkenyl group, it may be a monocyclic or an alkenyl group having a 2-4 cyclic structure. 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. 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, 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, it can be suitably dissolved in a solvent and can be suitably coated on a support plate.

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

<Method for manufacturing laminated body and method for manufacturing sealed body>
A method for manufacturing a laminated body according to an embodiment of the present invention comprises: sealing a sealing body that includes a wiring layer on which an element is mounted, the element, and a sealing material that seals the element. A method for producing a laminate, which comprises laminating an adhesive layer on a support for supporting the body, wherein the adhesive composition is applied on the support to form the adhesive layer. It includes a layer forming step. Here, the support is a support made of a material that transmits light, and a separation layer that is altered by irradiation with light is formed on the support before the step of forming the adhesive layer.

Moreover, the manufacturing method of the sealing body which concerns on one Embodiment of this invention is a manufacturing method of the said laminated body by the manufacturing method of the laminated body which concerns on one embodiment of this invention, and the said laminated body formation process. After that, by irradiating light through the support, the separation layer is altered to separate the support from the laminate, and after the separation step, the adhesive remaining on the sealing body side. And an adhesive layer removing step of removing the residue of the layer with a hydrocarbon solvent.

[Embodiment 1]
FIG. 1 is a diagram illustrating each step of the method for manufacturing a sealed body according to the first embodiment of the present invention. In the method for manufacturing the sealed body according to the present embodiment, the separation layer forming step, the adhesive layer forming step, the sealing body forming step, and the adhesive layer removing 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. 1B, 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 coating, slit coating, 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 polymerizable 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. The temperature is preferably vacuum or under an inert gas atmosphere such as nitrogen gas, and more preferably under an inert gas atmosphere such as nitrogen gas.

When the adhesive layer contains a photopolymerization initiator, the polymerizable 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.

[Sealing body forming process]
As shown in FIGS. 1C to 1F, in the sealing body forming step, the sealing body 7 is formed on the wiring layer 4. In the encapsulating body forming step of this embodiment, a wiring layer forming step, a mounting step, a sealing step, a thinning step, and an adhesive layer removing step are performed in this order.

[Wiring layer forming process]
As shown in FIG. 1C, in the wiring layer forming step, the wiring layer 4 is formed on the adhesive layer 3.

In one embodiment, as a procedure for forming the wiring layer 4, first, a dielectric layer such as silicon oxide (SiOx) or a photosensitive resin is formed on the adhesive layer 3. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin by 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 of 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.

As described above, when performing the photolithography process, the etching process, and the like, the adhesive layer 3 is exposed to an acid such as hydrofluoric acid, an alkali such as TMAH, and a resist solvent. In particular, in the fan-out type technique, cyclopentanone, cyclohexanone, etc. are used as the resist solvent in addition to PGMEA. However, the adhesive layer 3 has improved chemical resistance by polymerizing a polymerizable monomer in the block copolymer. Therefore, it is possible to prevent the adhesive layer 3 from being dissolved or peeled off by being exposed to the resist solvent as well as the acid and the alkali. Therefore, the wiring layer 4 can be preferably formed on the adhesive layer 3.

As shown in FIG. 1D, in the mounting process, the element 5 is mounted on the wiring layer 4. The element 5 can be mounted on the wiring layer 4 by using, for example, a chip mounter or the like.

As shown in FIG. 1E, in the sealing step, the element 5 is sealed with the sealing material 6. For reference, the sealing material 6 is injection-molded using a molding die while maintaining a high viscosity state, for example, while being heated to 100° C. or higher. Therefore, when sealing the element 5 with the sealing material 6, the adhesive layer 3 is pressed at a temperature of 100° C. or higher. However, the adhesive layer 3 has an increased dynamic complex elastic modulus when heated to a high temperature by polymerizing a polymerizable monomer in the block copolymer. Therefore, it is possible to prevent distortion in the sealing body 7 formed by sealing the element 5 with the sealing material 6 by being pressed at a temperature of 100° C. or higher. Therefore, the sealing body 7 can be preferably formed on the adhesive layer 3.

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 is a support 1 that transmits light, a separation layer 2 that is altered by irradiation with light, an adhesive layer 3, and a sealing body. 7 is laminated in this order, and the sealing body 7 is provided with the wiring layer 4 for mounting the element 5, the element 5, and the sealing material 6 for sealing the element 5, and the separation layer 2 Is covered with the adhesive layer 3 except for the portion in contact with the support 1. Such a laminate 8 is produced only in the process of the method for producing a laminate according to the present invention, and can be preferably used for producing the isolated sealing body 7.

[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 according to 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 body 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 the laser light irradiation conditions are not limited to these: 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 beam is preferably 100 mm/s or more and 10,000 mm/s or less.

Then, as shown in (i) of FIG. 1, in the separation step, the support 1 and the sealing body 7 are separated. For example, by applying a force in a direction in which the support 1 and the sealing body 7 are separated from each other, the support 1 and the sealing body 7 are separated. For example, one of the support 1 and the sealing body 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.

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

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

Further, the sealing body 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 (second 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. In the method for manufacturing a laminated body and the method for manufacturing a sealed body according to the second embodiment, a separation layer forming step, an adhesive layer forming step, a sealing body forming step, and a separation step cleaning step are performed in this order to obtain a sealing body. In the forming process, elements are arranged on the adhesive layer 3.

[Separation layer forming step to adhesive layer forming step]
As shown in FIGS. 2A and 2B, the separation layer forming step, the separation layer peripheral edge portion removing step, and the adhesive layer forming step are the same as those in the first embodiment, and thus the description thereof will be omitted.

[Sealing body forming process]
As shown in (c) to (f) of FIG. 2, in the sealing body forming step, the sealing body 7 is formed on the adhesive layer 3. In the encapsulating body forming step of this embodiment, the element arranging step, the encapsulating step, the thinning step, and the wiring layer forming step are performed in this order.

As shown in FIG. 2C, the element 5 is arranged on the adhesive layer 3 in the element arrangement step. The element 5 can be arranged on the adhesive layer 3 while the adhesive layer 3 is heated, for example, by using a chip mounter or the like.

As shown in FIG. 2D, in the sealing step, the element 5 is sealed with the sealing material 6. The sealing material 6 is injection-molded using, for example, a molding die. Needless to say, it is possible to prevent the adhesive layer 3 from being distorted when the element 5 is sealed in the sealing step, as in the case of the first embodiment.

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 wiring layer forming step, the wiring layer 4 is formed on the element 5 sealed with the sealing material 6.

In one embodiment, the wiring layer 4 can be formed in the same manner as in the first embodiment, and the description thereof will be 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 properties of the support 1. Separated from the laminate 9. Further, after that, in the cleaning step, the sealing body 7 can be obtained by removing the adhesive layer 3 using a hydrocarbon solvent as in the first embodiment ((i) in FIG. 2 ).

[Embodiment 3]
The third embodiment of the present invention will be described below. For convenience of description, members having the same functions as the members described in Embodiments 1 and 2 above will be given the same reference numerals and description thereof will be omitted. The method for manufacturing a laminated body and the method for manufacturing a sealing body according to the third embodiment include a separation layer forming step, a separation layer peripheral portion removing step, an adhesive layer forming step, a sealing body 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 process is the same as in the first and second embodiments, and thus the description thereof will be omitted.

[Separation layer peripheral edge removal step]
As shown in FIG. 3B, in the separation layer peripheral edge portion removing step, the separation layer 2 formed on the entire periphery of the peripheral edge portion 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 (c) of FIG. 3, 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. The method for forming the adhesive layer 3 is the same as in the first and second embodiments, and thus the description thereof is omitted.

[Sealing body forming process]
As shown in FIGS. 3D to 3G, in the sealing body forming step, the sealing body 7 ′ is formed on the adhesive layer 3. In the encapsulation body forming step of this embodiment, a wiring layer forming step, an element disposing step, a sealing step, and a thinning step are performed in this order.

As shown in FIG. 3D, in the third embodiment, in the wiring layer forming step, the outer peripheral end of the wiring layer 4 formed on the adhesive layer 3 is removed by trimming processing. The wiring 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 suitably performed on the laminated body 8'(FIG. 3).

Since the method of forming the wiring layer 4 is the same as that of the first and second embodiments, the description thereof will be omitted.

As shown in (e) to (g) of FIG. 3, also in the third embodiment, the element placement step, the sealing step, and the thinning step are performed. Note that the element placement step, the sealing step, and the thinning step in the third embodiment can be performed in the same manner as in the first embodiment, and therefore 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 body 7′ without the separation layer 2, so that the portion is By removing it, the support 1 and the sealing body 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 body 7'will always be Since it can be in a state of being bonded via the separation layer 2, the support 1 and the sealing body 7 ′ can be separated more smoothly when the quality of the separation layer 2 is changed.

[Separation process-Washing process]
As shown in (i) to (k) of FIG. 3, the sealing body 7′ can be manufactured by performing the separation step and the washing step as in the first embodiment.

(EBR processing)
In the (A) separation layer peripheral edge removing step, the EBR treatment for removing the separation layer 2 formed on the entire periphery of the support 1 in the peripheral portion 1b, and the (B) adhesive layer removing step, the support The EBR treatment for removing the adhesive layer 3 formed on the entire periphery 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. 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 therefore, a person skilled in the art, depending on the composition to be removed, It can be appropriately selected. For example, a terpene-based solvent such as p-menthane and a condensed ring hydrocarbon such as tetrahydronaphthalene can be used for the adhesive layer 3. For the separation layer 2, for example, a primary aliphatic amine such as monoisopropanolamine (MIPA), a secondary aliphatic amine such as 2-(methylamino)ethanol (MMA), triethanolamine, etc. At least one amine selected from the group consisting of tertiary aliphatic amines, alicyclic amines such as cyclohexylamine, aromatic amines such as benzylamine, and heterocyclic amines such as N-hydroxyethylpiperidine Alternatively, 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 rotational 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 easily study and determine the optimum conditions.

Further, it is preferable to dry the support 1 and the like after the object to be removed is dissolved 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 which 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 N ₂ 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 may be used alone, or any two or more methods may be used in combination.

[Embodiment 4]
The following will describe Embodiment 4 of the present invention. For convenience of description, members having the same functions as those 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 body according to Embodiment 4 include a separation layer forming step, a separation layer peripheral portion removing step, an adhesive layer forming step, a sealing body forming step, and an adhesive layer removing step. Carry out in order.

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

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

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

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

[Another embodiment]
The adhesive composition, the laminate, the method for producing the laminate, and the method for producing the sealing body according to the embodiment of the present invention are not limited to the above-described embodiments. In the above-described Embodiments 1 to 4, in the WLP technique, the support 1 having a circular shape in a top view can be preferably used as the support 1. However, in the technical field of semiconductor devices, in order to further increase the density of integration and improve production efficiency, in addition to increasing the size of the support 1 having a circular shape, a large panel having a rectangular shape in a top view is supported. It is being considered for use as a body. A method of manufacturing a semiconductor device using such a large quadrangular panel is known as a PLP (Panel level Package) technique and can be implemented by a fan-out type technique. Here, the adhesive composition according to an embodiment of the present application uses a curable adhesive composition containing a block copolymer and a polymerizable monomer to maintain high viscoelasticity when heated to a high temperature. can do. Therefore, even in the PLP (Panel level Package) technology in which the elements are arranged and sealed on the panel, it is possible to prevent the sealing body from being distorted. Therefore, the embodiment used in the fan-out type PLP technology is also within the scope of the present invention, the adhesive composition, the laminate, the method for producing the laminate, and the method for producing the sealing body according to the embodiment. In the PLP technology, a panel made of a material such as glass or silicon can be preferably used for the panel.

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.

<Example>
An adhesive composition was prepared using the following base polymer (block copolymer), curing monomer (polymerizable monomer), and polymerization initiator, and the chemical resistance of the adhesive layer formed using the adhesive composition. Also, the cleaning property was evaluated and the dynamic complex elastic modulus was measured.

[Preparation of adhesive composition and formation of adhesive layer]
[Example 1]
First, as the adhesive composition of Example 1, 80 parts by weight of Septon 2002 (base polymer: manufactured by Kuraray Co., Ltd., SEPS: styrene-isoprene-styrene triblock copolymer, styrene content 30%, molecular weight 53,000). ) And 20 parts by weight of tricyclodecane dimethanol diacrylate (curing monomer: "A-DCP (trade name)" manufactured by Shin-Nakamura Chemical Co., Ltd.)) are dissolved in 280 parts by weight of decahydronaphthalene to bond. The main ingredient of the agent composition was prepared. Then, as a curing agent, a dialkyl peroxide (thermal polymerization initiator: manufactured by NOF Corporation, “Parkmill D() was added so that the compounding amount with respect to 20 parts by weight of tricyclodecane dimethanol diacrylate was 0.4 parts by weight. (Trade name)") was dissolved in 20 parts by weight of butyl acetate. Then, the adhesive composition was prepared by blending the curing agent with the base resin.

Then, the adhesive composition of Example 1 is applied to a glass support (glass support, 8 inches, thickness 700 μm) by spin coating and baked at 90° C. and 140° C. for 5 minutes each. The solvent contained in the adhesive layer was removed by. Then, under a nitrogen gas atmosphere, the adhesive layer was heated at 200° C. for 1 hour to polymerize the curing monomer. As a result, the adhesive layer of Example 1 was formed (film thickness 5 μm). In addition, under the same conditions, an adhesive layer was formed on four glass supports, and each was used for evaluation of chemical resistance and evaluation of detergency.

(Evaluation of chemical resistance)
Evaluation of chemical resistance was carried out by immersing a glass support having an adhesive layer formed on each of cyclopentanone, cyclohexanone and PGMEA at 23° C. for 5 minutes, and then changing the weight of the laminate for each chemical. And the appearance change. The chemical resistance was evaluated as “◯” when there was no change in weight and appearance, and as “x” when there was a change in weight or appearance (presence of cracks). The results are shown in Table 1.

(Evaluation of detergency)
The glass support on which the adhesive layer of Example 1 was formed was rotated at 1,000 rpm, and p-menthane was supplied as a stripping solution to spin-clean the glass support. The presence or absence of residue on the glass support after washing was confirmed with a microscope. In addition, when there is a residue, the residue part is diffusely reflected by the high-intensity light emitted from the microscope and looks white. When a large amount of residue was observed, the detergency was evaluated as “x”, when almost no residue was observed, the detergency was evaluated as “△”, and when no residue was observed at all, Detergency was evaluated as “◯”. The results are shown in Table 1.

[Examples 2 to 32]
In Examples 2 to 32, a base resin, a curing monomer, and a polymerization initiator were mixed in a composition different from that of Example 1, and an adhesive layer was formed using these adhesive compositions. Then, under the same conditions as in Example 1, chemical resistance and detergency were evaluated. Tables 1 to 4 show the details of the compositions of Examples 2 to 32 and the respective evaluation results.

[Comparative Examples 1 and 2]
As Comparative Examples 1 and 2, an adhesive composition containing no curable monomer and a polymerization initiator was prepared, and the adhesive layer was not heated under the conditions of Example 1 at 200° C. for 1 hour. An adhesive layer was formed on the glass support by the same procedure as in 1. Further, under the same conditions as in Example 1, chemical resistance and detergency were evaluated. Table 5 shows the details of the compositions of Comparative Example 1 and Comparative Example 2 and the evaluation results.

The base polymers, curing monomers, and initiators used in Examples 2 to 32 and Comparative Examples 1 and 2 are as shown below.

[Base polymer]
-Styrene-isoprene-styrene triblock copolymer represented by the following chemical formula (9): SEPS (Kuraray Co., Ltd., "Septon 2002 (trade name)", styrene content 30%, molecular weight 53000).
-Styrene-isoprene-styrene triblock copolymer represented by the following chemical formula (9): SEPS (Kuraray Co., Ltd., "Septon 2004 (trade name)", styrene content 18%, molecular weight 90000)

[Curing monomer]
-Tricyclodecane dimethanol diacrylate represented by the following chemical formula (10) (Shin-Nakamura Chemical Co., Ltd., "A-DCP (trade name)")
-Tricyclodecane dimethanol dimethacrylate represented by the following chemical formula (11) (Shin-Nakamura Chemical Co., Ltd., "DCP (trade name)")

[Initiator]
Dialkyl peroxide (1 minute half temperature/175.2° C., 1 hour half temperature/135.7° C., theoretical active oxygen amount/5.92%: NOF CORPORATION, “Park Mill D (trade name)”)
-Peroxyester (1 minute half temperature/124.3°C, 1 hour half temperature/84.4°C, theoretical active oxygen amount/5.87%: manufactured by NOF Corporation, "Perocta O (trade name)")

(Evaluation results)
As shown in Tables 1 to 5, the adhesive layers of Examples 1 to 32 all had good chemical resistance to resist solvents such as cyclopentanone, cyclohexanone, and PGMEA (◯). On the other hand, the adhesive layers of Comparative Examples 1 and 2 containing no curing monomer had good chemical resistance to PGMEA, but low chemical resistance to cyclopentanone and cyclohexanone (x). From these results, it was possible to confirm that the wiring layers could be formed by performing photolithography on the glass support on which the adhesive layers of Examples 1 to 32 were formed.

Further, Examples 2 to 4, 6 to 8, 10 to 12, 14 to 16, 18 to 20, 22 to 24, 26 to 28 and 30 to 32, in which the content of the curing monomer is 15% by weight or less, It was excellent not only in chemical resistance but also in cleanability with p-menthane (○). Therefore, by increasing the content of the base polymer to more than 80% by weight and the content of the curing monomer to less than 20% by weight, an adhesive layer having not only high chemical resistance but also high detergency is formed. I was able to confirm that I could.

<Dynamic complex elastic modulus measurement test of adhesive layer>
The dynamic complex elastic modulus (E*) of the adhesive layer formed by each of the adhesive layer composition of Examples 2 and 6 and the adhesive compositions of Comparative Examples 1 and 2 was measured.

The adhesive composition of Example 2 was adjusted to a solid content concentration of 25% or more, spin-coated on a 6-inch Si wafer, baked at 90° C. and 140° C. for 5 minutes each, and then under a nitrogen atmosphere. The film was treated at 200° C. for 1 hour to form a 50 μm adhesive layer (film). The film was cut into a size of 20 mm (measurement width adjusted to 10 mm)×5 mm to obtain a test piece. The dynamic complex elastic modulus (E*) was measured from 50° C. at a temperature rising rate of 5° C./min at a frequency of 1 Hz using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.). The measurement was performed while increasing the temperature to 250°C. The results are shown in Table 9. The dynamic complex elastic moduli of the adhesive layers using the adhesive compositions of Example 6, Comparative Example 1 and Comparative Example 2 were measured under the same conditions as those of the adhesive composition of Example 2. The measurement results are shown in Table 6 below.

As shown in Table 6, it was confirmed that Examples 2 and 6 could maintain a high dynamic complex elastic modulus at a high temperature of 250°C. On the other hand, in the adhesive layers formed using the adhesive compositions of Comparative Examples 1 and 2, the samples were significantly softened at a high temperature of 200° C. or higher, and the dynamic complex elastic modulus could not be accurately measured. As a result, the adhesive layer cured with the curing monomer is prevented from being distorted even when pressure is applied particularly in a high temperature environment of 200° C. or higher, as compared with the adhesive layer without the curing monomer added. I was able to confirm that

<Evaluation of base polymer contained in adhesive layer>
The adhesive composition of Comparative Example 3 in which the base polymer S2004 in Comparative Example 2 was replaced with a cycloolefin polymer, and the adhesive composition of Comparative Example 4 in which the base polymer S2004 in Example 22 was replaced with a cycloolefin polymer. A composition was prepared. The adhesive layer of Comparative Example 4 was formed by the same procedure as in Example 22, and the adhesive layer of Comparative Example 3 was formed by the same procedure as in Comparative Example 2. Then, the dynamic complex elastic modulus (E*) in the adhesive layers of Example 22 and Comparative Examples 2 to 4 was measured. Further, the dissolution rates of the adhesive composition of Comparative Example 2 and the adhesive composition of Comparative Example 3 were measured in the adhesive layers formed by the adhesive compositions.

The compositions of the adhesive compositions of Comparative Examples 3 and 4 are shown in Table 7. As the base polymers of Comparative Examples 3 and 4, a cycloolefin polymer represented by the following chemical formula (12): “APL8008T (trade name)” manufactured by Mitsui Chemicals, Inc. (the following chemical formula (12), Mw=100, 000, Mw/Mn=2.1, m:n=80:20 (molar ratio)) were used.

(Dynamic complex elastic modulus measurement test of adhesive layer)
Regarding the adhesive layers using the adhesive compositions of Example 22, Comparative Example 3 and Comparative Example 4, the dynamic complex elastic modulus was measured under the same conditions as the adhesive composition of Comparative Example 2 described above. The measurement results are shown in Table 8 below.

As shown in Table 8, comparing the dynamic complex elastic moduli of the adhesive layers of Example 22 and Comparative Example 4, under the condition of 50° C., the adhesive layer of Comparative Example 4 has a higher dynamic complex elastic modulus. As shown, at the higher temperature of 150° C., the adhesive layer of Example 22 exhibits a higher dynamic complex elastic modulus. From this, it was confirmed that the adhesive layer of Example 22 could maintain a high dynamic complex elastic modulus even under higher temperature conditions. Even if the dynamic complex elastic moduli of the adhesive layers in Comparative Example 2 and Comparative Example 3 are compared, the adhesive layer of Comparative Example 2 using the block copolymer has a higher dynamic behavior at a higher temperature. The complex elastic modulus is maintained. Therefore, it was confirmed that the adhesive composition can maintain a high dynamic complex elastic modulus in a high temperature region by using the block copolymer as the base polymer.

(Measurement of dissolution rate)
The adhesive compositions of Comparative Examples 2 and 3 were applied to a glass support under the same conditions as in Example 1 and baked under the same conditions to form an adhesive layer (film thickness 5 μm). The support on which the adhesive layer was formed was dipped in p-menthane kept at 25° C., and the time until the adhesive layer was completely dissolved was measured. The dissolution rate (L/T (nm/sec)) was calculated from this dissolution time (T (sec)) and the thickness (L (nm)) of the adhesive layer measured in advance. Table 9 shows the measurement results of the dissolution rate.

As shown in Table 9, Comparative Example 2 in which the block copolymer was used as the base polymer had a faster dissolution rate than Comparative Example 3 in which the cycloolefin resin was used as the base polymer. From this result, it is clear that the adhesive layer using the block copolymer as the base polymer can be removed by washing more quickly than the cycloolefin polymer.

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 Wiring Layer 5 Element 6 Sealing Material 7, 7'Sealing Body 8, 8', 9, 9'Laminated Body

Claims (14)

A wiring layer on which an element is mounted, the above-mentioned element, and a sealing body including a sealing material for sealing the element are laminated on a support body supporting the sealing body via an adhesive layer. An adhesive composition for forming the adhesive layer in a laminated body comprising
In the above laminate, the support is a support that transmits light, and between the support and the adhesive layer, a separation layer that is altered by absorbing light is provided,
The adhesive composition,
A block copolymer,
A polymerizable monomer,
And a polymerization initiator,
The block copolymer, Ri hydrogenation product der triblock copolymer at both ends has a styrene block,
The polymerizable monomer has a hydrocarbon backbone (meth) adhesive composition characterized acrylate der Rukoto. The adhesive according to claim 1 , wherein the amount of the polymerizable monomer relative to the total amount of the block copolymer and the polymerizable monomer is in the range of 1% by weight or more and 50% by weight or less. Composition. Content of the styrene block of the said block copolymer is 10 weight% or more and 65 weight% or less, The adhesive composition of Claim 1 or 2 characterized by the above-mentioned. The weight average molecular weight of the block copolymer is 50,000 or more, the adhesive composition according to any one of claims 1 to 3, characterized in that at 150,000. The adhesive composition according to any one of claims 1 to 4, wherein the (meth)acrylic acid ester is a polyfunctional (meth)acrylic acid ester. The polymerization initiator, the adhesive composition according to any one of claims 1 to 5, characterized in that a thermal polymerization initiator or photopolymerization initiator. A wiring layer on which an element is mounted, the above-mentioned element, and a sealing body including a sealing material for sealing the element are laminated on a support body supporting the sealing body via an adhesive layer. A laminated body consisting of
In the above laminate, the support is a support that transmits light, and between the support and the adhesive layer, a separation layer that is altered by absorbing light is provided,
The adhesive layer is
A block copolymer,
A polymer of a polymerizable monomer,
And a polymerization initiator,
The block copolymer, Ri hydrogenation product der triblock copolymer at both ends has a styrene block,
The polymerizable monomer has a hydrocarbon backbone (meth) laminate, wherein the acrylic acid ester der Rukoto. The amount of the polymer of the polymerizable monomer relative to the total amount of the block copolymer and the polymer of the polymerizable monomer is in the range of 1% by weight or more and 50% by weight or less. 7. The laminated body according to 7 . Content of the styrene block of the said block copolymer is 10 weight% or more and 65 weight% or less, The laminated body of Claim 7 or 8 characterized by the above-mentioned. The laminate according to any one of claims 7 to 9 , wherein the block copolymer has a weight average molecular weight of 50,000 or more and 150,000 or less. The said (meth)acrylic acid ester polymer is a polyfunctional (meth)acrylic acid ester polymer, The laminated body as described in any one of Claims 7-10 characterized by the above-mentioned. A wiring layer on which an element is mounted, the above-mentioned element, and a sealing body including a sealing material for sealing the element are laminated on a support body supporting the sealing body via an adhesive layer. A method of manufacturing a laminated body comprising
In the layered product, the support is a support that transmits light, and between the support and the adhesive layer, a separation layer that is altered by absorbing light is formed,
An adhesive layer forming step of forming the adhesive layer by applying the adhesive composition according to any one of claims 1 to 6 on the separation layer. Manufacturing method of laminated body. A wiring layer on which an element is mounted, the above-mentioned element, and a sealing body including a sealing material for sealing the element are laminated on a support body supporting the sealing body via an adhesive layer. A method of manufacturing a laminated body comprising
In the laminate, the support is a support that transmits light, and between the support and the adhesive layer, a separation layer that is altered by absorbing light is formed,
An adhesive layer forming step of forming the adhesive layer by applying the adhesive composition according to claim 6 on the separation layer, and heating or exposing the laminate to produce a laminate. Method. The method for manufacturing a laminated body according to claim 12 or 13 , which includes a laminated body manufacturing step for manufacturing a laminated body,
After the laminated body manufacturing step, by irradiating the separation layer with light through the support, the separation layer is altered, and a separation step of separating the support from the laminated body,
A method of manufacturing a sealed body, comprising a cleaning step of removing the adhesive layer remaining on the sealed body side with a hydrocarbon solvent.

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