KR102254781B1 - An adhesive composition, a laminate, a method of manufacturing a laminate - Google Patents

Abstract

(Task) Provide an adhesive composition capable of forming an adhesive layer capable of maintaining high chemical resistance and maintaining high viscoelasticity at high temperatures as an adhesive composition used in a laminate for forming an encapsulant by means of a fan-out type technology. do.
(Solution means) The adhesive composition is a laminate formed by laminating an encapsulant including a wiring layer on which an element is mounted, an element, and an encapsulant for encapsulating the element, on a support supporting the encapsulant through an adhesive layer. In the adhesive composition for forming the adhesive layer, the adhesive composition contains a block copolymer, a polymerizable monomer, and a polymerization initiator.

Description

Adhesive composition, laminate, and manufacturing method of laminate {AN ADHESIVE COMPOSITION, A LAMINATE, A METHOD OF MANUFACTURING A LAMINATE}

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

As a semiconductor package (semiconductor device) containing a semiconductor element (electronic component), a wafer level package (WLP) or the like is known. In semiconductor packages such as WLP and PLP, a fan doll technology such as fan doll WLP (Fan-in Wafer Level Package), in which terminals at the ends of bare chips are rearranged in the chip area, and terminals other than the chip area are provided. A fan-out type technology such as a fan-out type WLP (Fan-out Wafer Level Package) for rearrangement is known. In particular, the fan-out type technology is applied to a fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged and packaged on a panel, and because it realizes integration, thinness and miniaturization of semiconductor devices, these Fan-out-type technology such as is attracting attention.

Patent Document 1 describes 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 light diffusing pressure-sensitive adhesive composition containing a quaternary ammonium compound. have.

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

In Patent Document 3, a resin composition containing a chain polymerizable monomer, a crosslinking agent that crosslinks through a sequential reaction, and a crosslinkable polymer having a crosslinkable group reacting with the crosslinking agent is prepared by chain polymerization and sequential crosslinking reaction. Having a crosslinked crosslinked relief forming layer on a support, the storage modulus E'(MPa) of the crosslinked relief forming layer at a frequency of 100 Hz at 25°C satisfies the relationship of 1 ≤ E'≤ 30, and 25 A laser engraving type flexographic printing plate original plate has been described in which the maximum elongation L (%) at the time of tensile fracture in °C satisfies the relationship of 30≦L≦300.

Patent Document 4 includes a substrate to be ground, a bonding layer in contact with the substrate to be ground, a light-to-heat conversion layer containing a light absorber and a thermally decomposable resin, and a light-transmitting support, provided that the light-to-heat conversion layer, A laminate is described in which the surface of the substrate on the opposite side to the bonding layer is ground and then decomposed when irradiated with radiant energy to separate the ground substrate and the light-transmitting support.

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

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

However, in Patent Documents 1 to 5, in the fan-out type technology, an adhesive layer capable of maintaining high viscoelasticity when heated to a high temperature and having high chemical resistance required when manufacturing a sealing member is provided. No disclosure has been made regarding the adhesive composition that can be formed.

In the fan-out type technology, the present inventors have high chemical resistance and can form an adhesive layer capable of maintaining high viscoelasticity when heated to a high temperature by using a curable adhesive composition containing a block copolymer and a polymerizable monomer. , The adhesive layer was found to be useful in order to form a sealing body, and the present invention was completed.

The present invention has been made in view of the above-described problems, and its object is an adhesive composition used in a laminate for forming an encapsulant by a fan-out type technology, which has high chemical resistance and is high at high temperatures. It is to provide an adhesive composition capable of forming an adhesive layer capable of maintaining viscoelasticity and a related technology thereof.

In order to solve the above problem, the adhesive composition according to the present invention comprises a wiring layer on which an element is mounted, and an encapsulant including an encapsulant for encapsulating the element and the element, on a support for supporting the encapsulant. An adhesive composition for forming the adhesive layer in a laminate formed by laminating through an adhesive layer, wherein the adhesive composition contains a block copolymer, a polymerizable monomer, and a polymerization initiator.

In addition, in the laminate according to the present invention, an encapsulant including a wiring layer on which an element is mounted, and an encapsulant for encapsulating the element and the element is laminated on a support for supporting the encapsulant via an adhesive layer. As a laminate thus obtained, the adhesive layer is characterized in that it comprises a block copolymer, a polymer of a polymerizable monomer, and a polymerization initiator.

According to the present invention, as an adhesive composition used in a laminate for forming an encapsulant by a fan-out type technology, an adhesive composition capable of forming an adhesive layer capable of having high chemical resistance and maintaining high viscoelasticity at high temperatures And the related technology can be provided.

1 is a diagram illustrating a method of manufacturing a laminate according to Embodiment 1 of the present invention.
2 is a diagram illustrating a method of manufacturing a laminate according to Embodiment 2 of the present invention.
3 is a diagram for explaining a method of manufacturing a laminate according to Embodiment 3 of the present invention.
4 is a diagram illustrating a method of manufacturing a laminate according to Embodiment 4 of the present invention.

<Adhesive composition>

The adhesive composition according to the present invention is formed by laminating an encapsulant comprising a wiring layer on which an element is mounted, and an encapsulant for encapsulating the element and the element, on a support supporting the encapsulant via an adhesive layer. It is an adhesive composition for forming the said adhesive layer in a laminated body. In other words, it is an adhesive composition for forming on the support a wiring layer on which an element is mounted, and an adhesive layer for forming an encapsulation body including the element and an encapsulant for sealing the element on the support.

The adhesive composition contains a block copolymer and a polymerizable monomer as a resin composition for forming an adhesive layer, a polymerization initiator that polymerizes the polymerizable monomer, and a diluting solvent for adjusting the coating workability of the resin composition. Includes. In addition, it is more preferable that the adhesive composition employs a resin composition composed of a block copolymer and a polymerizable monomer as a resin composition for forming an adhesive layer.

The adhesive composition is placed in a heated or pressure-sensitive environment to remove a diluting solvent, and polymerizable monomers are polymerized with a polymerization initiator in a block copolymer to form an adhesive layer. Since the adhesive layer contains a block copolymer, it has high chemical resistance, and by polymerizing a polymerizable monomer, when heated to a high temperature, high viscoelasticity, that is, a high dynamic complex elastic modulus can be maintained. Accordingly, it is possible to form an adhesive layer that can be suitably used in a fan-out type technique that requires forming a wiring layer using various resist solvents and sealing an element with an encapsulant at high temperature.

[Block copolymer]

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

The block copolymer is preferably a diblock copolymer or a triblock copolymer, and more preferably a triblock copolymer. Further, a diblock copolymer and a triblock copolymer may be used in combination.

Moreover, in the block copolymer, the terminal of the block copolymer may be modified with a functional group by using a modifier. Here, as the functional group, for example, an amino group, an acid anhydride group (preferably a maleic anhydride group), an imide group, a urethane group, an epoxy group, an imino group, a hydroxyl group, a carboxyl group, a silanol group, and an alkoxysilane group (the alkoxy group has carbon number of It is preferable that it is 1-6). In this way, the block copolymer modified with the modifier is an elastomer and has a functional group having polarity. For this reason, the flexibility and adhesion of the adhesive layer can be improved.

Moreover, it is preferable that the block copolymer contains a styrene block, and it is more preferable that it is a triblock copolymer in which both ends of a main chain are styrene blocks. By using a triblock copolymer in which styrene blocks are disposed at both ends, the thermal stability of the adhesive layer can be improved.

As a block copolymer containing a styrene block, a styrene-olefin type block copolymer is mentioned, for example.

As the styrene-olefin block copolymer, for example, 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-ethylene-ethylene-propylene-styrene block copolymer in which the styrene block is a reactive crosslinked type (Septon V9461 ( Kuraray Co., Ltd.), Septon V9475 (Kuraray Co., Ltd.)), a styrene-ethylene-butylene-styrene block copolymer in which a styrene block is a reactive crosslinked type (Septon V9827 (manufactured by Kuraray Co., Ltd.), having a reactive polystyrene hard block) , And polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification), and the like.

Moreover, it is preferable that a block copolymer is a hydrogenated substance, More specifically, it is more preferable that it is a hydrogenated substance of a block copolymer of a styrene block and a conjugated diene block. By using the hydrogenated product of the block copolymer, the stability against heat can be improved, and deterioration such as decomposition or polymerization can be made difficult to occur. In addition, it can bring about high compatibility with hydrocarbon-based solvents, and can bring about low compatibility with resist solvents, that is, high resistance to resist solvents.

As a commercial item that can be used as a block copolymer, for example, Kuraray Co., Ltd. ``Cepton (brand name)'', Kuraray Co., Ltd. ``Hybra (brand name)'', Asahi Chemical Co., Ltd. ``Tuftec (brand name)'' and "Dynaron (brand 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 exhibits a tendency to maintain a high dynamic complex modulus when heated to a high temperature as the content of the styrene block increases. In addition, the smaller the content of the styrene block is, the higher the compatibility with the hydrocarbon-based solvent can be obtained.

Moreover, it is preferable that it is 50,000 or more and 150,000 or less, and, as for the weight average molecular weight of a block copolymer, it is more preferable that it is 60,000 or more and 120,000 or less. The block copolymer exhibits a tendency to maintain a high dynamic complex modulus when heated to a higher temperature as the weight average molecular weight is larger. Moreover, as the weight average molecular weight is smaller, the tendency to obtain high compatibility with, for example, a hydrocarbon-based solvent is exhibited.

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

For example, when Septon4033 of Cepton (brand name) manufactured by Kuraray Co., Ltd., having a styrene unit content of 30% by weight, and Septon2063 of Septon (brand name), having a styrene unit content of 13% by weight, are mixed at a weight ratio of 1 to 1, The styrene content with respect to the entire block copolymer contained in the adhesive is 21 to 22% by weight, and therefore, is 10% by weight or more. Further, for example, when a styrene unit of 10% by weight and 60% by weight are mixed at a weight ratio of 1 to 1, it becomes 35% by weight, and falls within the above range. The present invention may be in such a form. Moreover, it is most preferable that the plural kinds 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 can be swelled and partially dissolved with a hydrocarbon-based solvent, and is easily removed. can do. In addition, high resistance to resist solvents used in resist lithography (e.g., propylene glycol monomethyl ether acetate (PGMEA), etc.), acids (hydrofluoric acid, etc.), and alkali tetramethylammonium hydroxide (TMAH) can be obtained. have. In addition, 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 a base resin, and viscoelasticity at high temperatures are improved. By doing so, it is possible to reduce the blending amount of the polymerizable monomer described later.

As the amount of the block copolymer contained in the adhesive composition, for example, the total amount of the block copolymer and the polymerizable monomer is 100% by weight, preferably within the range of 50% by weight or more and 99% by weight or less, and 60% by weight. The inside of the range of at least 95% by weight is more preferable, and the inside of at least 80% by weight and at most 95% by weight 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, in the adhesive layer, high compatibility with a hydrocarbon-based solvent derived from block copolymerization can be maintained, and Removal by washing can be facilitated.

[Polymerizable monomer]

The adhesive composition contains a polymerizable monomer. The polymerizable monomer is preferably a monomer polymerized by radical polymerization, and typically, a polyfunctional (meth)acrylic acid ester is exemplified.

As the polyfunctional (meth)acrylic acid ester, a bifunctional or higher (meth)acrylic acid ester may be used, or a trifunctional or higher polyfunctional (meth)acrylic acid ester may be used. By using a bifunctional or trifunctional or higher (meth)acrylic acid ester, in the block copolymer of the adhesive layer, a three-dimensional network structure by the polymer of the (meth)acrylic acid ester can be suitably formed, and chemical resistance in the adhesive layer can be improved. It can be improved, and the viscoelasticity of the adhesive layer when heated to a high temperature, that is, the dynamic complex elastic modulus can be improved.

As the bifunctional (meth)acrylic acid ester, polyethylene glycol diacrylate having a weight average molecular weight of 200 or more and 1000 or less in the main chain, and polypropylene glycol diacrylate having a weight average molecular weight of 50 or more and 700 or less in the polypropylene glycol main chain. Acrylate and polyether di(meth)acrylates such as polyethylene glycol dimethacrylate having a degree of polymerization of 1 or more and 23 or less of the oxyethylene constituent units, and ethoxylation in which the polymerization degree of the oxyethylene constituent units is 3 or more and 30 or less Bisphenol-type diacrylates such as bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A diacrylate with a polymerization degree of 2.3 or more and 30 or less. (Meth)acrylate is mentioned. Further, ethoxylated polypropylene glycol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2,2bis[4-(methacryloxyethoxy)phenyl]propane, 9,9- Di(meth)acrylates having an ether skeleton such as bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, glycerin dimethacrylate, and polytetramethylene glycol diacrylate. Cyclodecanedimethanoldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, And di(meth)acrylates having a carbon skeleton such as neopentyl glycol di(meth)acrylate or a cyclic hydrocarbon skeleton.

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

As a commercial item that can be used as a bifunctional (meth)acrylic acid ester, for example, Shin-Nakamura Chemical Co., Ltd. ``701A (brand name)'', ``A-200 (brand name)'', ``A-400 (brand name)'', ``A-600 (brand name)'', ``A-1000 (brand name)'', ``A-B1206PE (brand name)'', ``ABE-300 (brand name)'', ``A-BPE-10 (brand name)'', ``A- BPE-20 (brand name)'', ``A-BPE-30 (brand name)'', ``A-BPE-4 (brand name)'', ``A-BPEF (brand name)'', ``A-BPP-3 (brand name)'', ``A-DCP (brand name)'', ``A-DOD-N (brand name)'', ``A-HD-N (brand name)'', ``A-NOD-N (brand name)'', ``APG-100 (brand name)'' , ``APG-200 (brand name)'', ``APG-400 (brand name)'', ``APG-700 (brand name)'', ``A-PTMG-65 (brand name)'', ``1G (brand name)'', ``2G (brand name) )'', ``3G (brand name)'', ``4G (brand name)'', ``9G (brand name)'', ``14G (brand name)'', ``23G (brand name)'', ``BPE-80N (brand name)'', ``BPE- 100 (brand name)'', ``BPE-200 (brand name)'', ``BPE-500 (brand name)'', ``BPE-900 (brand name)'', ``BPE-1300N (brand name)'', ``DCP (brand name)'', `` DOD-N (brand name)", "HD-N (brand name)", "NOD-N (brand name)", "NPG-N (brand name)", "1206PE (brand name)", "701 (brand name)" and " 9PG (brand name)", etc. are mentioned.

As a commercial item that can be used as a polyfunctional (meth)acrylic acid ester, for example, Shin-Nakamura Chemical Co., Ltd. "A-9300 (brand name)", "A-9300-1CL (brand name)", and "A-GLY- 9E (brand name)'', ``A-GLY-20E (brand name)'', ``A-TMM-3 (brand name)'', ``A-TMM-3-L (brand name)'', ``A-TMM-3LM-N ( ``A-TMPT (brand name)'', ``AD-TMP (brand name)'', ``ATM-35E (brand name)'', ``A-TMMT (brand name)'', ``A-9550 (brand name)'', `` A-DPH (brand name)" and "TMPT (brand name)", etc. are mentioned.

As the amount of the polymerizable monomer contained in the adhesive composition, for example, the total amount of the block copolymer and the polymerizable monomer is 100% by weight, preferably within a range of 1% by weight or more and 50% by weight or less, and 1% by weight In the range less than% or more and 20% by weight, it is more preferable. As the amount of the polymerizable monomer increases, the dynamic complex elastic modulus can be increased when the adhesive layer is heated to a high temperature. In addition, it is possible to increase the chemical resistance of the adhesive layer, and in particular, resistance to resist solvents such as cyclohexanone, cyclopentanone, and N-methyl-2-pyrrolidone (NMP) as well as PGMEA can be improved. In addition, as the amount of the polymerizable monomer decreases, the adhesive layer can maintain high cleaning properties when a hydrocarbon-based solvent derived from a block copolymer is used. Therefore, the adhesive composition is to increase the dynamic complex modulus of the block copolymer itself by adjusting the content and weight average molecular weight of the styrene block in the block copolymer, and to increase the dynamic complex modulus by mixing a relatively small amount of polymerizable monomer. desirable. In particular, high viscoelasticity is maintained by mixing a polymerizable monomer within a range of 1% by weight or more and less than 20% by weight by making the total amount of the block copolymer and the polymerizable monomer 100% by weight, and easily by a solvent. At first glance, it is possible to solve both of the problems that can be taken as a trade-off.

In addition, in polyfunctional (meth)acrylic acid ester, monofunctional (meth)acrylic acid ester, and, for example, urethane (meth)acrylate, epoxy ( You may use together polymerizable monomers, such as meth)acrylate, styrene, divinylbenzene, and vinyl acetate.

(Complex modulus of elasticity of the adhesive layer)

The adhesive layer formed from the adhesive composition has a high complex elastic modulus when heated at a high temperature by a block copolymer and a polymer of a polymerizable monomer. For this reason, on the adhesive layer, deformation of the adhesive layer can be prevented in an environment of high temperature (100°C or higher, 400°C or lower) and high pressure (10 kgf or higher) when forming the sealing body. Here, although the complex elastic modulus (E*) of the adhesive layer formed by the adhesive composition varies depending on the temperature conditions to be adapted, for example, it is preferably 1000 Pa or more, and more preferably 10000 Pa or more. When the dynamic complex modulus (E*) of the adhesive layer is 10000 Pa or more at a temperature adapted for forming the encapsulant, in the high-temperature process, deformation of the adhesive layer when pressure is applied can be more suitably prevented. . In addition, the dynamic complex elastic modulus (E*) spin coats the adhesive composition on a 6-inch Si wafer to form a film (adhesive layer) of a predetermined thickness. A sample may be prepared by peeling the film and cutting it into a predetermined size. In addition, the dynamic complex elastic modulus (E*) may be measured while heating the sample under conditions of a frequency of 1 Hz and at a temperature rising rate of 5° C./min to a temperature equal to or higher than the temperature assumed at the time of forming the sealing body. For example, if the temperature assumed at the time of forming the sealing body is about 100 to 200°C, for example, the dynamic complex elastic modulus (E*) may be measured while increasing the temperature from 50°C to 250°C.

(Dilution solvent)

The diluting solvent contained in the adhesive composition may be any one capable of dissolving a block copolymer and a polymerizable monomer, and for example, a non-polar hydrocarbon-based solvent, a polar and non-polar petroleum-based solvent, and the like can be used.

Preferably, the diluting solvent may contain a condensed polycyclic hydrocarbon. When the solvent contains a condensed polycyclic hydrocarbon, clouding that may occur when the adhesive composition is stored in a liquid form (especially at low temperatures) can be avoided and product stability can be improved.

Examples of the hydrocarbon-based solvent include linear, branched or cyclic hydrocarbons. For example, linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane, branched hydrocarbons having 3 to 15 carbon atoms; p-mentane, o-mentane, Saturated aliphatic hydrocarbons such as m-mentane, diphenylmentane, 1,4-terpine, 1,8-terpine, bornane, norbornane, refuge, tuyan, karan, and longipolene, α-terpinene, β- Terpinene, γ-terpinene, α-pinene, β-pinene, α-twoon, β-twoon, and the like.

Moreover, as a petroleum solvent, cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, etc. are mentioned, for example.

In addition, the condensed polycyclic hydrocarbon is a condensed ring hydrocarbon formed by two or more monocycles sharing only one side of each ring, and it is preferable to use a hydrocarbon formed by condensation of two monocyclic rings.

Examples of such hydrocarbons include a combination of a five-membered ring and a six-membered ring, or a combination of two six-membered rings. Examples of the hydrocarbon in which a five-membered ring and a six-membered ring are combined include indene, pentalene, indane, tetrahydroindene, and the like, and as a combination hydrocarbon of two six-membered rings, for example, Naphthalene, tetrahydronaphthalene (tetraline), decahydronaphthalene (decalin), and the like.

In addition, when the diluting solvent contains the condensed polycyclic hydrocarbon, the component contained in the solvent may be only the condensed polycyclic hydrocarbon, and may contain other components such as, for example, a saturated aliphatic hydrocarbon. In this case, the content of the condensed polycyclic hydrocarbon is preferably 40 parts by weight or more, and more preferably 60 parts by weight or more, when the total amount of the hydrocarbon-based 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-based solvent contains a condensed polycyclic hydrocarbon and a saturated aliphatic hydrocarbon, the odor of the condensed polycyclic hydrocarbon can be alleviated.

In addition, 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, when the total amount of the adhesive composition is 100 parts by weight, 20 It is preferably in the range of not less than 90 parts by weight and not more than 90 parts by weight. When the content of the diluting solvent is within the above range, viscosity adjustment becomes easy.

[Polymerization initiator]

The polymerization initiator may polymerize the above-described polymerizable monomer, and is not particularly limited, but a thermal polymerization initiator or a photopolymerization initiator is preferable, and a thermal polymerization initiator is more preferable.

(Thermal polymerization initiator)

As a thermal polymerization initiator, a peroxide, an azo polymerization initiator, etc. are mentioned, for example. These thermal polymerization initiators polymerize a polymerizable monomer by radicals generated by heating.

Examples of the peroxide include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy ester, peroxy carbonate and peroxy ketal. Specifically, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl-2-methylpropyl-1- Hydroperoxide, pertriphenylacetate-tert-butyl, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, and 4-methoxy Tert-butyl acetate and tert-butyl perN-(3-toluyl)carbamic acid, dicumyl-peroxide, tert-butyl-peroxy-2-ethylhexyl-monocarbonate, di(4-tert-butylcyclo Hexyl)peroxydicarbonate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,1-di(tert-butylperoxy)cyclohexane, etc. are mentioned.

As a commercially available peroxide, for example, the brand name "Percumyl (registered trademark)" manufactured by Nippon Oil Co., Ltd., the brand name "Perbutyl (registered trademark)", the brand name "Perocta (registered trademark)", and "Perroil ( Registered trademark)" and "Perhexa (registered trademark)", and the like.

As an azo polymerization initiator, for example, 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'-azobisisobutylamide , 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate methyl, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis -2-Methylbutyronitrile, 2,2'-dimethyl azobisisobutyrate, 1,1'-azobis(1-methylbutyronitrile-3-sodium sulfonate), 2-(4-methylphenylazo)-2 -Methylmalonodinitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvalero Nitrile, 4,4'-azobis-4-dimethyl cyanovalerate, 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-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobi Scumene, 4-nitrophenylazobenzylcyanoethyl acetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane And poly(bisphenol A-4,4'-azobis-4-cyanopentanoate) and poly(tetraethylene glycol-2,2'-azobisisobutyrate).

The blending amount of the thermal polymerization initiator is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 5 parts by weight or less, based on 100 parts by weight of the polymerizable monomer. Accordingly, the polymerizable monomer contained in the adhesive layer can be suitably polymerized. In addition, the thermal polymerization initiator may be blended into the adhesive composition by a known method immediately before using the adhesive composition. In addition, the thermal polymerization initiator may be mixed with the adhesive composition after being diluted in an additive solvent described later.

It is preferable that it is 90 degreeC or more and 200 degreeC or less, and, as for the 1 minute half-life temperature of a thermal polymerization initiator, it is more preferable that it is 120 degreeC or more and 180 degreeC or less.

Moreover, it is preferable that it is 50 degreeC or more and 140 degreeC or less, and, as for the 1 hour half-life temperature of a thermal polymerization initiator, it is more preferable that it is 80 degreeC or more and 140 degreeC or less.

Since the one-minute half-life temperature of the thermal polymerization initiator is 90°C or higher and 200°C or lower, and the one-hour half-life temperature is 50°C or higher and 140°C or lower, the polymerizable monomer is polymerized and gelled after the thermal polymerization initiator is blended. You can lengthen the time until. Accordingly, it is possible to lengthen the workable time when applying the adhesive composition on the support. In addition, when the one-minute half-time temperature of the thermal polymerization initiator is 90°C or higher and 200°C or lower, and the one-hour half-life temperature is 50°C or higher and 140°C or lower, the adhesive composition is applied on the support and heated to remove the diluted solvent. At the same time, radicals can be generated and polymerization of the polymerizable monomer can be preliminarily started. From the viewpoint of extending the workable time, the one-minute half-life temperature and the 1-hour half-life temperature of the thermal polymerization initiator are preferably higher. Further, from the viewpoint of rapidly gelling, the one-minute half-life temperature and the 1-hour half-life temperature of the thermal polymerization initiator are preferably lower.

Moreover, it is preferable that the theoretical amount of active oxygen of the thermal polymerization initiator is 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 has high chemical resistance and high heat resistance by polymerizing a polymerizable monomer with a photoinitiator, and can form an adhesive layer having high cleaning properties. In addition, when a photopolymerization initiator is used as the polymerization initiator, if the adhesive composition is packaged so as to maintain a light-shielding state, the adhesive composition can be commercialized in a state in which the photopolymerization initiator is blended.

As a photoinitiator, specifically, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydro Roxyethoxy)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)-butane- 1-one, ethanol 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzoyldi Phenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2 -Ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) Oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 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-mercaptobenzoimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4 ,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-di Phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer , 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (I.e. Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 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, benzo-t-butyl ether, acetophenone, 2,2-die Toxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, pt-butyltrichloroacetophenone, pt- Butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, benzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenyl Acridine, 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-ethoxystyryl)-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-trichloro Methyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s -Triazine and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. In addition, as a photopolymerization initiator, commercially available products "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651" and "IRGACURE 907" (brand names: all manufactured by BASF) and "NCI-831" (brand names: ADEKA), etc. can also be used.

The blending amount of the photopolymerization initiator is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 5 parts by weight or less, based on 100 parts by weight of the polymerizable monomer.

(Additive solvent)

It is preferable that a thermal polymerization initiator and a photopolymerization initiator are dissolved in an additive solvent and blended into the adhesive composition. Although it does not specifically limit as an additive solvent, An organic solvent which dissolves the component contained in an adhesive composition can be used.

As the organic solvent, for example, each component of the adhesive composition may be dissolved and a homogeneous solution may be used, and only one organic solvent may be used, or two or more organic solvents may be used in combination.

Specific examples of the organic solvent include, for example, a terpene solvent having an oxygen atom, a carbonyl group, or an acetoxy group as a polar group. For example, geraniol, nerol, linalol, citral, citrone Lol, menthol, isomentol, neomentol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1, 4-cineol, 1,8-cineol, borneol, carbon, yonone, tuyon, and camphor are mentioned. In addition, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene Polyhydric alcohols such as glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyhydric alcohols or the above Derivatives of polyhydric alcohols, such as monoalkyl ethers of compounds having an ester bond, monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether, or compounds having ether bonds such as monophenyl ether (in particular, propylene Glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, and pyruvic acid Esters such as methyl, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; Aromatic organics such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol and butylphenyl ether Solvents, etc. are mentioned.

The content of the additive solvent may be appropriately adjusted according to the type of the thermal polymerization initiator and the photopolymerization initiator. For example, when the total of the diluting solvent (main solvent) and the additive solvent that dissolves the resin component is 100 parts by weight, it is added. The content of the solvent is preferably 1 part by weight or more and 50 parts by weight or less, and more preferably 1 part by weight or more and 30 parts by weight or less. When the content of the additive solvent is within the above range, the thermal polymerization initiator and the photopolymerization initiator can be sufficiently dissolved.

<Laminate>

A laminate according to an embodiment of the present invention includes a wiring layer on which an element is mounted, an encapsulant including an encapsulant for encapsulating the element and the element, and an adhesive layer interposed on a support for supporting the encapsulant. As a laminate obtained by laminating, 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 a laminate according to an embodiment of the present invention, an adhesive layer is formed using the adhesive composition according to an embodiment of the present invention. For this reason, on the adhesive layer formed on a support body, a wiring layer can be formed suitably, and an element can be sealed suitably. Accordingly, a laminate in which an adhesive layer is formed using the adhesive composition according to an embodiment of the present invention is also a scope of the present invention.

[Enclosure]

The sealing member includes a wiring layer on which an element is mounted, an element, and a sealing material that seals the element. It is preferable that the sealing member is provided with a plurality of elements, and by dicing such a sealing member, a plurality of electronic components can be obtained.

(Wiring layer)

The wiring layer is also called RDL (Redistribution Layer: redistribution layer), is a thin-film wiring body constituting a wiring connected to an element, and may have a single-layer or multiple-layer structure. In one embodiment, the wiring layer is a dielectric (e.g., a photosensitive resin such as silicon oxide (SiOx), a photosensitive epoxy, etc.), a conductor (e.g., aluminum, copper, titanium, nickel, gold, silver, etc.) The wiring may be formed by a metal and an alloy such as a silver-tin alloy), but is not limited thereto.

(device)

The device is a semiconductor device or other device, and may have a single-layer or multiple-layer structure. In addition, when the element is a semiconductor element, the electronic component obtained by dicing the sealing member becomes a semiconductor device.

(Encapsulation)

As the sealing material, for example, a sealing material containing an epoxy resin can be used. It is preferable that the encapsulant is not formed for each element, but integrally encapsulates all of the plurality of elements mounted on the wiring layer.

[Support]

The support should have the necessary strength to prevent damage or deformation of each constituent element of the sealing body at the time of formation of the sealing body. Further, the support is formed of a material that transmits light having a wavelength capable of deteriorating the separation layer formed on the support.

As the material of the support, for example, glass, silicone, acrylic resin, etc. can be used, but the material is not limited thereto. 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 to fix the encapsulant on the support and to protect the separation layer.

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 explanation is omitted.

Moreover, as a polymer of a polymerizable monomer, it is preferable that it is a polymer of polyfunctional (meth)acrylic acid ester. Since the polyfunctional (meth)acrylic acid ester is the same as that described above, explanation is omitted.

The thickness of the adhesive layer may be appropriately set according to the type of the support and the encapsulant, and the treatment performed when forming the encapsulation, but it is preferably 0.1 µm or more and 50 µm or less, and more preferably 1 µm or more and 10 µm or less. Do. When it is 1 micrometer or more, the sealing body can be suitably fixed on a support body. By being 10 micrometers or less, it is possible to facilitate the removal of the adhesive layer in a subsequent step.

[Separation layer]

The separation layer is a layer that is deteriorated by irradiation with light. The support can be separated from the encapsulant by irradiating light to the separating layer through the support to denature the separating layer.

In addition, in the present specification, the ``deterioration'' of the separating layer means a state in which the separating layer can be destroyed by receiving a slight external force, or a phenomenon in which the adhesion between the layer in contact with the separating layer is lowered. . As a result of the deterioration of the separating layer caused by absorbing light, the separating layer loses strength or adhesiveness before being irradiated with light. That is, by absorbing light, the separation layer is softened. The deterioration of the separation layer may mean that the separation layer causes decomposition by energy of absorbed light, changes in three-dimensional arrangement, or dissociation of functional groups. Deterioration of the separation layer occurs as a result of absorbing light.

Thus, for example, the support plate and the substrate can be easily separated by deforming so that the separation layer is destroyed just by lifting the support plate. More specifically, for example, one of the substrate and the support plate in the laminate is fixed to a mounting table by means of a support separation device or the like, and an adsorption pad (adsorption unit) provided with adsorption means, etc. The support plate and the substrate are separated by holding the other side by lifting the support plate, or the chamfered portion at the end of the circumferential edge portion of the support plate is grasped by a separating plate equipped with a clamp (pole portion), and a force is applied to the substrate. Just remove the support plate. Further, for example, the support plate may be peeled from the substrate in the laminate by means of a support body separating device provided with a peeling means for supplying a peeling solution for peeling the adhesive. By supplying a peeling solution to at least a part of the peripheral end of the adhesive layer in the laminate by the peeling means, and swelling the adhesive layer in the laminate, the force is concentrated on the separation layer from the place where the adhesive layer swells, Force can be applied to the substrate and support plate. For this reason, it is possible to suitably separate the substrate and the support plate.

The force applied to the laminate may be appropriately adjusted according to the size of the laminate, but is not limited, for example, if a laminate having a diameter of about 300 mm, by applying a force of about 0.1 to 5 kgf, the substrate and the substrate The support plate can be properly removed.

The thickness of the separation layer is, for example, more preferably in the range of 0.05 µm or more and 50 µm or less, and still more preferably in the range of 0.3 µm or more and 1 µm or less. If the thickness of the separating layer falls within the range of 0.05 µm or more and 50 µm or less, desired deterioration can be caused in the separating layer by irradiation of light for a short period of time and light of low energy. Moreover, it is particularly preferable that the thickness of the separation layer falls within the range of 1 µm or less from the viewpoint of productivity.

Further, another layer may be further formed between the separation layer and the support. In this case, the other layer may be made of a material that transmits light. Accordingly, a layer having desirable properties or the like can be appropriately added without interfering with the incidence of light to the separation layer. Depending on the type of material constituting the separation layer, the wavelength of light that can be used is different. Therefore, the material constituting the other layer does not need to transmit all light, and can be appropriately selected from materials capable of transmitting light of a wavelength capable of deteriorating the material constituting the separation layer.

In addition, the separation layer is preferably formed of only a material having a light-absorbing structure, but within a range that does not impair the essential properties in the present invention, a material not having a light-absorbing structure is added. , You may form a separation layer. In addition, it is preferable that the surface of the separation layer on the side opposite to the adhesive layer is flat (no irregularities are formed), and thus, the separation layer can be easily formed, and also in affixing. It becomes possible to apply uniformly.

(Fluorocarbon)

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

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

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

(Polymer containing a structure having light absorbing property in its repeating unit)

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

The structure having light absorption is a chemical structure that absorbs light and denatures a polymer containing the structure as a repeating unit. The structure is, for example, an atomic group containing a conjugated π electron system composed of a substituted or unsubstituted benzene ring, a condensed ring, or a heterocycle. More specifically, the structure is a cardo structure or a benzophenone structure present in the side chain of the polymer, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenylsulfone structure), a diphenyl structure or diphenylamine. It can be a structure.

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

[Formula 1]

(Wherein, R is each independently an alkyl group, an aryl group, halogen, hydroxyl group, ketone group, sulfoxide group, sulfone group or N(R ⁴ )(R ⁵ ), wherein R ⁴ and R ⁵ are each independently Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is not present or is -CO-, -SO ₂ -, -SO- or -NH-, and n is 0 or an integer of 1 to 5 .)

In addition, the polymer contains, for example, a repeating unit represented by any of (a) to (d) in the following formulas, or is represented by (e), or the structure of (f) is Included in the main chain.

[Formula 2]

(Wherein, l is an integer greater than or equal to 1, m is an integer of 0 or 1 to 2, X is any of the formulas shown in the above "formula 1" in (a) to (e), and in (f) In the above, any of the formulas shown in "Formula 1" or not present, Y ₁ and Y ₂ are each independently -CO- or -SO ₂ -l is preferably an integer of 10 or less. )

Examples of the benzene ring, condensed ring and heterocycle represented by the above "Formula 1" include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, Substituted acridine, azobenzene, substituted azobenzene, fluorim, substituted fluorim, 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, carboxyl It is selected from acid, carboxylic acid ester, sulfonic acid, sulfonic acid ester, alkylamino and arylamino.

Among the substituents represented by the above "Chemical Formula 1", _{examples of the case where Z is -SO 2} -as the fifth substituent having two phenyl groups are 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(3- Hydroxyphenyl)sulfone, bis(2-hydroxyphenyl)sulfone, and bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, and the like.

Among the substituents represented by the above "Chemical Formula 1", examples of the case where Z is -SO- as the fifth substituent having two phenyl groups are 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-dihydro) Roxyphenyl)sulfoxide, bis(2,3,4-trihydroxyphenyl)sulfoxide, bis(2,3,4-trihydroxy-6-methylphenyl)-sulfoxide, bis(5-chloro-2, 3,4-trihydroxyphenyl)sulfoxide, bis(2,4,6-trihydroxyphenyl)sulfoxide, bis(5-chloro-2,4,6-trihydroxyphenyl)sulfoxide, etc. are mentioned. I can.

Among the substituents represented by the above "Chemical Formula 1", examples of the case where Z is -C(=O)- as the fifth substituent having two phenyl groups are 2,4-dihydroxybenzophenone, 2,3 ,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',5,6'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy Benzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydro Roxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethylamino-2'-hydroxy Benzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2',4'-dihydroxy Benzophenone, and 4-dimethylamino-3',4'-dihydroxybenzophenone, etc. are 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 within a range in which the light transmittance of the separation layer is 0.001% or more and 10% or less. If the polymer is prepared so that the ratio falls within such a range, the separating layer sufficiently absorbs light, so that it can be deteriorated reliably and quickly. That is, removal of the support body from the sealing body is easy, and the light irradiation time required for the removal can be shortened.

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

Light that the above structure can absorb is, for example, a high-pressure mercury lamp (wavelength: 254 nm or more, 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser Light emitted from (wavelength: 157 nm), XeCl laser (wavelength: 308 nm), XeF laser (wavelength: 351 nm) or solid UV laser (wavelength: 355 nm), or g-line (wavelength: 436 nm), h It is a line (wavelength: 405 nm) or i-line (wavelength: 365 nm).

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

(Inorganic)

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

The inorganic material may have a configuration that is deteriorated by absorbing light, and for example, one or more types of inorganic materials selected from the group consisting of metals, metal compounds, and carbon can be suitably 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 are not limited thereto, but are selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more types of inorganic substances can be mentioned. In addition, the term carbon is a concept in which an allotrope of carbon may also be included, and for example, it may be diamond, fullerene, diamond-like carbon, carbon nanotube, or the like.

The inorganic material absorbs light having a wavelength in an inherent range depending on the type. By irradiating the separation layer with light having a wavelength in a range absorbed by the inorganic material used in the separation layer, the inorganic material can be suitably denatured.

As the light irradiated to the separation layer made of inorganic material, depending on the wavelength at which the inorganic material can be absorbed, for example, _{solid-state lasers such as YAG laser, ruby laser, glass laser, YVO 4} laser, LD laser, fiber laser, and dye laser A liquid laser such as a CO ₂ laser, an excimer laser, an Ar laser, a gas laser such as a He-Ne laser, a laser light such as a semiconductor laser or a free electron laser, or a non-laser light may be appropriately used.

The separation layer made of an inorganic material can be formed on the support by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating. The thickness of the separation layer made of inorganic material is not particularly limited, and any film thickness capable of sufficiently absorbing the light to be used may be sufficient. For example, it is more preferable to set it as a film thickness within the range of 0.05 µm or more and 10 µm or less. Further, an adhesive may be previously applied to both sides or one side of an inorganic film (eg, a metal film) made of an inorganic material constituting the separation layer, and adhered to the support.

In addition, when a metal film is used as the separation layer, depending on conditions such as the film quality of the separation layer, the type of laser light source, and laser output, the reflection of the laser or charging to the film may occur. Therefore, it is preferable to take countermeasures against them by forming an antireflection film or an antistatic film above or below the separation layer or on either side.

(Compound having an infrared absorbing structure)

The separation layer may be formed of a compound having an infrared absorbing structure. The compound is deteriorated by absorbing infrared rays. As a result of the deterioration of the compound, the separation layer loses strength or adhesiveness before being irradiated with infrared rays. Therefore, by applying a slight external force (for example, lifting the support, etc.), the separation layer is destroyed, and the support and the sealing member can be easily separated.

As a compound containing a structure having infrared absorption or a structure having infrared absorption, for example, alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, cyclic Type), alkyne (1-substituted, 2-substituted), monocyclic aromatic (benzene, 1-substituted, 2-substituted, 3-substituted), alcohols and phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary, saturated Tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane cyclic ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 -Enol of diketone, o-hydroxyaryl ketone, dialkylaldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, Lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride (conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, primary Amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary 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, nitroamine , Nitrosoamine, nitrate ester, nitrite ester, nitroso bond (aliphatic, aromatic, monomer, dimer), mercaptan and sulfur compounds such as thiophenol and thiol acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, Primary sulfonamide, secondary sulfonamide, sulfuric ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is, H, C, O or halogen), PA ² bond (A ² is, H, C Or O), or It may be a Ti-O bond.

As a structure including the carbon-halogen bond, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , aryl fluoride, and aryl chloride.

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 etc. are mentioned. As a structure containing a Si-A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

As a structure including the PA ² bond, PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is aliphatic or aromatic), (A ⁴ O ) _3- PO (A ⁴ is alkyl), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH and O=P-OH.

The above structure can absorb infrared rays having a desired range of wavelengths depending on the type of selection. Specifically, the wavelength of infrared rays that the structure can absorb is within a range of, for example, 1 µm or more and 20 µm or less, and more suitably absorbs within a range of 2 µm or more and 15 µm or less. In addition, when the structure is a Si-O bond, a Si-C bond, and a Ti-O bond, it may be in the range of 9 µm or more and 11 µm or less. In addition, the wavelength of infrared rays capable of absorbing each structure can be easily understood by those skilled in the art. For example, as the absorption band in each structure, non-patent literature: SILVERSTEIN, BASSLER, MORRILL, "Identification method by spectrum of organic compounds (5th edition) -Combination of MS, IR, NMR, and UV-" (1992 Published in the year) You can refer to the description on pages 146 to 151.

As a compound having an infrared absorbing structure used for formation of the separation layer, among the compounds having the structure as described above, it can be dissolved in a solvent for application and solidified to form a high-rise. If there is one, it is not particularly limited. However, in order to effectively deteriorate the compound in the separation layer and facilitate separation of the support and the encapsulant, the absorption of infrared rays in the separation layer is large, that is, the transmittance of infrared rays when the separation layer is irradiated with infrared rays. It is desirable that this is low. Specifically, the infrared transmittance in the separation layer is preferably lower than 90%, and more preferably the infrared transmittance is 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 formula (1) and a repeating unit represented by the following formula (2), or a resin represented by the following formula (1) A resin which is a copolymer of a repeating unit and a repeating unit derived from an acrylic compound can be used.

[Formula 3]

(In 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, t-butylstyrene (TBST)-dimethylsiloxane copolymer, which is a copolymer of the repeating unit represented by the above formula (1) and the repeating unit represented by the following formula (3), is more preferred, A TBST-dimethyl siloxane copolymer comprising 1:1 of the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (3) is more preferred.

[Formula 4]

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

[Formula 5]

(In formula (4), R ⁷ is hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms, and in formula (5), R ⁸ is an alkyl group having 1 or more and 10 or less carbon atoms, or a phenyl group.)

In addition, as a compound having a silsesquioxane skeleton, Japanese Unexamined Patent Publication No. 2007-258663 (published on October 4, 2007), Japanese Unexamined Patent Publication No. 2010-120901 (published on June 3, 2010), Each silsesquioxane resin disclosed in Japanese Unexamined Patent Publication No. 2009-263316 (published on November 12, 2009) and Japanese Unexamined Patent Publication No. 2009-263596 (published on November 12, 2009) suitably Can be used.

Among them, as the compound having a silsesquioxane skeleton, a copolymer of a repeating unit represented by the following formula (6) and a repeating unit represented by the following formula (7) is more preferable, and a repeating unit represented by the following formula (6) And a copolymer containing a repeating unit represented by the following general formula (7) at 7:3.

[Formula 6]

As a polymer having a silsesquioxane skeleton, there may be a random structure, a ladder structure, and a basket structure, but any structure may be used.

In addition, as a compound containing a Ti-O bond, for example, (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy) titanium, and titanium Alkoxy titanium, such as -i-propoxy octylene glycolate; (ii) Chelate titanium, such as di-i-propoxy bis (acetylacetonato) titanium, and propanedioxy titanium bis (ethylacetoacetate); (iii ) iC ₃ H ₇ O-[-Ti(OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ , and nC ₄ H ₉ O-[-Ti(OnC ₄ H ₉ ) ₂ -O-] _{n Titanium polymers such as -nC 4} H ₉ ; (iv) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, and (2-n-butoxycarbonyl Acylate titanium, such as benzoyloxy) tributoxy titanium; (v) Water-soluble titanium compounds, such as di-n-butoxy bis (triethanol aminato) titanium, etc. are mentioned.

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

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

(Infrared absorbing material)

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

The infrared-absorbing material may have a configuration that changes by absorbing infrared rays, and, for example, carbon black, iron particles, or aluminum particles can be suitably used. The infrared absorbing material absorbs light having a wavelength in its own range depending on its type. By irradiating the separation layer with light having a wavelength in a range absorbed by the infrared absorbing material used for the separation layer, the infrared absorbing material can be suitably denatured.

(Reactive polysilsesquioxane)

The separation layer can be formed by polymerizing reactive polysilsesquioxane. Accordingly, 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, and the silanol group Alternatively, they can be polymerized with each other by condensing a functional group capable of forming a silanol group. In addition, the reactive polysilsesquioxane is a reactive poly having a silsesquioxane skeleton such as a random structure, a cage structure, and a ladder structure, provided that it has a silanol group or a functional group capable of forming a silanol group. Silsesquioxane can be employed.

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

[Formula 7]

In formula (8), R′ is each independently selected from the group consisting of hydrogen and an alkyl group having 1 or more and 10 or less carbon atoms, and more preferably selected from the group consisting of hydrogen and an alkyl group having 1 or more and 5 or less carbon atoms. Do. When R'is hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms, the reactive polysilsesquioxane represented by the general formula (8) can be suitably condensed by heating in the separation layer forming step.

In the general 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. Reactive polysilsesquioxane has a higher content of Si-O bonds than those formed using other materials, and is preferably infrared (0.78 µm or more, 1,000 µm or less), by having a repeating unit represented by the formula (8). Preferably, a separation layer having high absorbance at a far infrared ray (3 µm or more and 1,000 µm or less), more preferably 9 µm or more and 11 µm or less, can be formed.

In addition, in the general formula (8), R'is each independently the same or different organic groups. Here, R is, for example, an aryl group, an alkyl group, an alkenyl group, and 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, etc. are mentioned, and it is more preferable that it is a phenyl group. Further, the aryl group may be bonded to the polysilsesquioxane skeleton through an alkylene group having 1 to 5 carbon atoms.

When R'is an alkyl group, examples of the alkyl group include a linear, branched, or cyclic alkyl group. Moreover, when R is an alkyl group, it is preferable that it is 1-15, and, as for carbon number, it is more preferable that it is 1-6. Moreover, when R is a cyclic alkyl group, an alkyl group having a monocyclic or 2-4 cyclic structure may be used.

When R'is an alkenyl group, as in the case of an alkyl group, a linear, branched, or cyclic alkenyl group is exemplified, and the alkenyl group preferably has 2 to 15 carbon atoms, and 2 to 6 It is more preferable that it is. Moreover, when R is a cyclic alkenyl group, an alkenyl group having a monocyclic or 2-4 cyclic structure may be used. As an alkenyl group, a vinyl group, an allyl group, etc. are mentioned, for example.

Moreover, as a substituent which R'may have, a hydroxyl group, an alkoxy group, etc. are mentioned. When the substituent is an alkoxy group, a linear, branched, or cyclic alkylalkoxy group is exemplified, and the number of carbon atoms in the alkoxy group is preferably 1 to 15, and more preferably 1 to 10.

In addition, in one aspect, the siloxane content of the reactive polysilsesquioxane is preferably 70 mol% or more and 99 mol% or less, and more preferably 80 mol% or more and 99 mol% or less. When the siloxane content of the reactive polysilsesquioxane is 70 mol% or more and 99 mol% or less, it is appropriately deteriorated by irradiating 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 possible separation layer.

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

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

<The manufacturing method of a laminated body and the manufacturing method of a sealing body>

In a method for manufacturing a laminate according to an embodiment of the present invention, an encapsulant including a wiring layer on which an element is mounted, the element, and an encapsulant for encapsulating the element is provided on a support for supporting the encapsulant. A method for producing a laminate formed by laminating through an adhesive layer, comprising a step of forming an adhesive layer by applying the adhesive composition described above on the support. Here, the support is a support made of a material that transmits light, and before the bonding layer forming step, a separation layer that is deteriorated by irradiating light is formed on the support.

In addition, the manufacturing method of the encapsulation body according to the embodiment of the present invention includes a layered body manufacturing step of manufacturing the layered body and the layered body forming step by the production method of the layered body according to the embodiment of the present invention. Thereafter, by irradiating light through the support, the separation layer is denatured, thereby separating the support from the laminate, and after the separation step, the residue of the adhesive layer remaining on the side of the encapsulant is removed from a hydrocarbon-based solvent. It includes an adhesive layer removing step to remove by.

[Embodiment 1]

1: is a figure explaining each process of the manufacturing method of a sealing body of Embodiment 1 of this invention. In the method of manufacturing a sealing member according to the present embodiment, a separation layer forming step, an adhesive layer forming step, a sealing member forming step, and an adhesive layer removing step are performed in this order.

[Separation layer formation process]

As shown in Fig. 1(a), in the separation layer formation step, light is applied to one plane portion 1a of the support 1 that transmits light, for example, by chemical vapor deposition (CVD) method or the like. The separation layer 2 which is deteriorated by irradiation is formed. In addition, "one plane part" refers to one of the plane parts which the support body 1 has. Moreover, the "planar part" may have minute irregularities of a degree that can be regarded as a substantially flat surface.

[Adhesive layer formation process]

As shown in (b) of FIG. 1, in the adhesive layer formation step, the adhesive composition described above is applied and heated by, for example, a method such as spin coating, dipping, roller blade, spray coating, slit coating, or the like, Alternatively, the diluted solvent contained in the adhesive composition is removed by placing it in a pressure-sensitive environment. Thereafter, when the adhesive layer contains a thermal polymerization initiator, the polymerizable monomer contained in the adhesive layer may be polymerized by heating. In addition, conditions for heating the adhesive layer 3 may be appropriately set based on the 1 minute half-life temperature and the 1-hour half-time temperature in the thermal polymerization initiator, for example, 50°C or more and 300°C or less. At a temperature within the range, it is preferable to perform under vacuum or in an inert gas atmosphere such as nitrogen gas, and more preferably under an inert gas atmosphere such as nitrogen gas.

In addition, when the adhesive layer contains a photoinitiator, the polymerizable monomer contained in the adhesive layer may be polymerized by exposure under an inert gas atmosphere such as nitrogen gas. In addition, the conditions for exposure may be appropriately set according to the kind of the photoinitiator.

[Encapsulation Formation Process]

As shown to (c) to (f) of FIG. 1, in the sealing body forming step, the sealing body 7 is formed on the wiring layer 4. In the sealing body forming process in this embodiment, a wiring layer forming process, a mounting process, a sealing process, a thinning process, and an adhesive layer removal process are performed in this order.

[Wiring layer formation process]

As shown in FIG. 1(c), in the wiring layer formation process, the wiring layer 4 is formed on the adhesive layer 3.

In one embodiment, in the order of formation of the wiring layer 4, first, a dielectric layer such as silicon oxide (SiOx) and 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 evaporation method, or the like. The dielectric layer made of a photosensitive resin can be formed by applying a 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 by a conductor such as metal. As a method of forming the wiring, for example, a known semiconductor process method such as a lithography treatment such as photolithography (resist lithography) and an etching treatment can be used.

In this way, when performing a photolithography treatment, an etching treatment, or 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 technology, as a resist solvent, in addition to PGMEA, cyclopentanone, cyclohexanone, and the like are used. However, the adhesive layer 3 has improved chemical resistance by polymerizing a polymerizable monomer in the block copolymer. For this reason, it is possible to prevent dissolution or peeling of the adhesive layer 3 by exposure to not only acids and alkalis, but also a resist solvent. Accordingly, the wiring layer 4 can be suitably formed on the adhesive layer 3.

As shown in FIG. 1(d), in the mounting process, the element 5 is mounted on the wiring layer 4. Mounting of the element 5 onto the wiring layer 4 can be performed using, for example, a chip mounter or the like.

As shown in FIG. 1(e), in the sealing process, the element 5 is sealed with the sealing material 6. It is not particularly limited, and for reference, the sealing material 6 is injection-molded using a molding die while maintaining a high viscosity state while being heated to, for example, 100° C. or higher. For this reason, 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 a high dynamic complex elastic modulus when heated to a high temperature by polymerizing a polymerizable monomer in the block copolymer. For this reason, by pressing at a temperature of 100° C. or higher, it is possible to prevent deformation from occurring in the sealing member 7 formed by sealing the element 5 with the sealing material 6. Therefore, on the adhesive layer 3, the sealing body 7 can be formed suitably.

As shown in FIG. 1(f), in the thinning process, the sealing material 6 is thinned. The sealing material 6 may be thinned to a thickness equal to that of the element 5, for example.

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

The laminate 8 shown in Fig. 1(g) obtained by the above process includes a support 1 that transmits light, a separation layer 2 that is deteriorated by irradiation with light, an adhesive layer 3, and a rod. The retainer 7 is laminated in this order, and the encapsulant 7 includes a wiring layer 4 for mounting the element 5, an element 5, and a sealing material 6 that seals the element 5 ), and the separation layer 2 is covered with an adhesive layer 3 except for a portion in contact with the support 1. Such a layered product 8 is manufactured only in the process of the manufacturing method of the layered product according to the present invention, and can be suitably used in order to manufacture the isolated encapsulant 7.

[Separation process]

As shown in FIG. 1(h), in the separation step, the separation layer 2 is deteriorated by irradiating light L to the separation layer 2 through the support 1. The type and wavelength of the light L to be irradiated may be appropriately selected according to the transmittance of the support 1 and the material of the separation layer 2, for example, YAG laser, ruby laser, glass laser, YVO ₄ laser, Solid-state lasers such as LD lasers and fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, excimer lasers, Ar lasers, gas lasers such as He-Ne lasers, laser light such as semiconductor lasers, free electron lasers, or non- Laser light can be used. Thereby, the separating layer 2 can be deteriorated, and the support 1 and the sealing body 7 can be easily separated from each other.

In addition, examples of the laser light irradiation conditions in the case of irradiating laser light include the following conditions, but are not limited thereto: The average output value of the laser light is preferably 1.0 W or more and 5.0 W or less, and 3.0 It is more preferable that it is W or more and 4.0 W or less; The repetition frequency of laser light is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less; The scanning speed of laser light is 100 mm/s It is more preferably 10,000 mm/s or less.

Thereafter, as shown in Fig. 1(i), in the separation step, the support 1 and the sealing member 7 are separated. For example, the support 1 and the sealing body 7 are separated by applying a force in a direction in which the support 1 and the sealing body 7 are separated from each other. For example, in a state in which one of the support 1 and the sealing member 7 is fixed to the stage, the other is lifted while being sucked and held by a separating plate provided with an adsorption pad such as a bellows pad. And the sealing member 7 can be separated.

(Washing process)

As shown in FIG. 1(h), in the washing step, the adhesive layer 3 and the separation layer 2 remaining on the sealing member 7 from which the support 1 has been separated are removed. For example, a washing step of removing residues of the adhesive layer 3 and the separation layer 2 is performed with a washing liquid containing an organic solvent or the like. The adhesive layer (3) may preferably use a diluting solvent used in the adhesive composition, that is, a hydrocarbon-based solvent, as a cleaning liquid, and in particular, a terpene-based solvent such as p-mentane, and a condensed cyclic hydrocarbon such as tetrahydronaphthalene. It is more preferable to use.

By the above, the isolated sealing body 7 can be obtained.

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

[Embodiment 2]

Another embodiment (Embodiment 2) of the present invention will be described below. In addition, for convenience of description, members having the same functions as those described in the above embodiment are denoted by the same reference numerals, and the description thereof is omitted. In the manufacturing method of the laminated body and the sealing body according to the second embodiment, a separation layer forming step, an adhesive layer forming step, a sealing member forming step, and a separation step washing step are performed in this order, and in the sealing body forming step, An element is placed on the adhesive layer (3).

[Separation layer formation process-adhesive layer formation process]

As shown in FIGS. 2A and 2B, since the separation layer forming step, the separation layer circumferential portion removing step, and the adhesive layer forming step are the same as those of the first embodiment, their descriptions are omitted.

[Encapsulation Formation Process]

As shown in FIG. 2(c)-(f), in the sealing body formation process, the sealing body 7 is formed on the adhesive layer 3. In the sealing body formation process in this embodiment, an element arrangement process, a sealing process, a thinning process, and a wiring layer formation process are performed in this order.

As shown in FIG. 2C, in the element arrangement process, the element 5 is placed on the adhesive layer 3. Arrangement of the element 5 on the adhesive layer 3 can be performed in a state where the adhesive layer 3 is heated, for example, using a chip mounter or the like.

As shown in FIG. 2D, in the sealing process, the element 5 is sealed with the sealing material 6. The sealing material 6 is injection-molded using, for example, a molding die. In addition, as in the case of the first embodiment, it is needless to say that deformation can be prevented from occurring in the adhesive layer 3 when sealing the element 5 in the sealing step.

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

As shown in FIG. 2F, in the wiring layer formation process, the wiring layer 4 is formed on the element 5 sealed by the sealing material 6.

In one embodiment, since the wiring layer 4 can be formed in the same manner as in the first embodiment, the description thereof will be omitted.

By the above process, the laminated body 9 can be obtained like Embodiment 1.

Thereafter, as shown in (g) and (h) of FIG. 2, in the separation step, by irradiating light from the support 1 toward the separation layer 2 to denature the separation layer 2, the support ( 1) is separated from the laminate (9). In addition, after that, in the washing step, as in the first embodiment, the sealing member 7 can be obtained by removing the adhesive layer 3 using a hydrocarbon-based solvent (FIG. 2(i)).

[Embodiment 3]

It is as follows when Embodiment 3 of this invention is demonstrated. In addition, for convenience of explanation, members having the same functions as those described in the first and second embodiments are denoted by the same reference numerals, and the description thereof is omitted. In the manufacturing method of the laminated body and the sealing body according to the third embodiment, a separation layer forming step, a separation layer circumferential part removal step, an adhesive layer forming step, an encapsulant forming step, and an adhesive layer removing step are performed in this order. .

[Separation layer formation process]

As shown in FIG. 3(a), since the separation layer formation process is the same as that of the first and second embodiments, the description thereof will be omitted.

[Separation layer peripheral edge removal process]

As shown in (b) of FIG. 3, in the separation layer peripheral edge portion removal step, separation formed around the entire peripheral edge portion 1b of the support 1 by, for example, EBR (Edge Bead Removal) treatment. Remove layer (2). The peripheral edge portion 1b is a peripheral edge portion of the flat portion 1a. Accordingly, as shown in Fig. 3(b), the separation layer 2 is formed on the flat portion 1a in a portion surrounded by the peripheral edge portion 1b from which the separation layer 2 has been removed. Becomes. Details of the EBR process will be described later.

[Adhesive layer formation 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 side from which the separation layer 2 around the entire circumference 1b is removed. do. Accordingly, the entire surface of the separation layer 2 formed on the support 1 is covered with the adhesive layer 3. In addition, since the method of forming the adhesive layer 3 is the same as that of the first and second embodiments, the description thereof will be omitted.

[Encapsulation Formation 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 sealing body formation process in this embodiment, a wiring layer formation process, an element arrangement process, a sealing process, and a thinning process 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 a trimming treatment. In addition, the trimming of the wiring layer 4 may be removed by grinding by a known means such as a grinder. Thereby, in the subsequent process, EBR treatment can be suitably performed in the laminated body 8'(FIG. 3).

In addition, 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 to (e)-(g) of FIG. 3, also in Embodiment 3, an element arrangement process, a sealing process, and a thinning process are implemented. In addition, since the element arrangement process, the sealing process, and the thinning process in Embodiment 3 can be implemented similarly to Embodiment 1, the description is abbreviate|omitted.

[Adhesive layer removal process]

As shown in FIG. 3(h), in the adhesive layer removing step, the adhesive layer 3 formed around the entire circumference 1b of the support 1 is removed by, for example, EBR treatment. Of the adhesive layer 3, the portion formed around the entire circumferential edge portion 1b of the support 1 adheres the support 1 and the sealing member 7 ′ without the separation layer 2 interposed therebetween. , When the separation layer 2 is deteriorated by removing the portion, the support 1 and the sealing member 7'can be smoothly separated.

In particular, by removing the adhesive layer 3 formed outside the outer circumferential end 2a of the separating layer 2 formed on the support 1, the support 1 and the encapsulant 7'must be separated from each other. (2) Since it can be made into a state of being bonded via the interposition, when the separation layer 2 is deteriorated, the support 1 and the sealing member 7'can be separated more smoothly.

[Separation process-washing process]

As shown to (i)-(k) of FIG. 3, similarly to Embodiment 1, the sealing body 7'can be manufactured by performing a separation process and a washing process.

(EBR treatment)

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

The solvent used in the method of removing with a solvent may be any one capable of dissolving the separation layer 2 or the adhesive layer 3 to be removed, and is not particularly limited. You can choose appropriately. For example, for the adhesive layer 3, in particular, terpene-based solvents such as p-mentane, and condensed cyclic hydrocarbons such as tetrahydronaphthalene can be used. In addition, for the separation layer 2, for example, primary aliphatic amines such as monoisopropanolamine (MIPA), secondary aliphatic amines 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, or, A solvent or the like containing them can be used. In addition, organic solvents other than a terpene solvent can be used suitably among what was illustrated in the column of the above-mentioned (additive solvent) as a solvent.

As a method of supplying a solvent, a method of supplying a solvent to an object to be removed by spraying of the solvent, and a method of immersing the object to be removed in a solvent are mentioned, for example.

As a method of supplying the solvent to the object to be removed by spraying the solvent, a method of supplying the solvent to the object to be removed while rotating the support 1 is preferable in order to supply the solvent uniformly. As a method of supplying the solvent while rotating the support 1, for example, a nozzle for ejecting the solvent is disposed immediately on the outside of the circumferential edge portion 1b of the support 1, and the solvent is placed on the support ( A method of rotating the support 1 using a spinner is mentioned while dropping it on the immediately outside of the circumferential edge portion 1b of 1). Thereby, the solvent can be supplied just outside the entire circumference of the circumferential edge portion 1b of the support 1. In addition, there is no limit to the number of nozzles to be arranged, and one or more may be sufficient.

In the above method involving rotation of the support 1 and ejection of the solvent, the rotation speed of the support 1, the flow rate of the solvent when supplying the solvent from the nozzle, and the supply time of the solvent are determined by the composition of the object to be removed and the removal time. Although it may differ depending on the thickness of the object, the kind of solvent to be used, and the degree of removal, those skilled in the art can examine and determine the optimum conditions without difficulty.

In addition, it is preferable to dry the support 1 or the like after dissolution of the object to be removed with a solvent. By passing through the drying process, it is possible to remove an unnecessary solvent and a solvent that has penetrated into the separation layer 2 or the adhesive layer 3 that is not a part to be removed.

As a drying method, the support body 1 is rotated using a spinner, etc., and drying _{by air blow by spraying of N 2} gas, drying by baking, drying by reduced pressure, etc. I can. In addition, as these drying methods, any method may be used alone, or any two or more methods may be used in combination.

[Embodiment 4]

It is as follows when Embodiment 4 of this invention is demonstrated. In addition, for convenience of explanation, members having the same functions as those described in the above-described Embodiments 1 to 3 are denoted by the same reference numerals, and the description thereof is omitted. In the manufacturing method of the laminated body and the sealing body according to the fourth embodiment, a separation layer forming step, a separation layer circumferential part removal step, an adhesive layer forming step, an encapsulant forming step, and an adhesive layer removing step are performed in this order. .

[Separation layer formation process-adhesive layer formation process]

Since the separation layer formation process, the separation layer circumference part removal process, and the adhesive layer formation process are the same as those of the third embodiment, their explanations are omitted.

[Encapsulation Formation Process]

In the sealing body formation process, the element 5 is arrange|positioned on the adhesive layer 3, and it seals. That is, the sealing body 7'is formed by the same process as Embodiment 2. After that, as shown in Fig. 4A, the outer peripheral end of the sealing member 7'is removed by a trimming treatment. In addition, the trimming of the sealing member 4 may be removed by grinding by a known means such as a grinder. Accordingly, in the subsequent step, the EBR treatment can be suitably performed in the layered product 9'(FIG. 4).

[Adhesive layer removal process]

As shown in (b) of FIG. 4, in the same manner as in the third embodiment, in the fourth embodiment, by trimming the outer peripheral end of the sealing member 7', more than the outer peripheral end 2a of the separating layer 2 The adhesive layer 3 formed on the outside can be removed. For this reason, when the separation layer 2 is deteriorated, the support 1 and the sealing member 7'can be separated more smoothly.

Thereafter, similarly to Embodiments 1 to 3, the sealing body 7'can be manufactured by removing the adhesive layer 3 with a hydrocarbon-based solvent.

[Other embodiments]

The adhesive composition, the laminated body, the production method of the laminated body, and the sealing body production method according to one embodiment of the present invention are not limited to the above-described embodiment. In the above-described Embodiments 1 to 4, in the WLP technology, as the support 1, the support 1 having a circular shape as viewed from the top surface can be suitably used. However, in the technical field of semiconductor devices, in addition to increasing the size of the circular support 1, it is considered to use a large-sized panel having a rectangular shape when viewed from the top as a support for higher density integration and improved production efficiency. Has become. A method of manufacturing a semiconductor device using such a large rectangular panel is known as a panel level package (PLP) technology, and can be implemented by a fan-out type technology. Here, the adhesive composition according to the embodiment of the present application can maintain high viscoelasticity when heated to a high temperature by using a curable adhesive composition containing a block copolymer and a polymerizable monomer. For this reason, also in the PLP (Panel level Package) technology in which elements are arranged and sealed on a panel, it is possible to prevent deformation from occurring in the sealing member. Therefore, the embodiment used in the fan-out type PLP technology, the adhesive composition, the laminated body, the production method of the laminated body, and the sealing body according to the embodiment are also the scope of the present invention. In addition, in the PLP technology, a panel formed of a material such as glass or silicon can be suitably used for the panel.

The present invention is not limited to each of the above-described embodiments, but various modifications are possible within the scope indicated in the claims, and the technical scope of the present invention also applies to embodiments obtained by appropriately combining the technical means disclosed in each of the different embodiments. Included.

Example

<Example>

An adhesive composition was prepared using a base polymer (block copolymer), a curing monomer (polymerizable monomer), and a polymerization initiator shown below, and evaluation of chemical resistance and cleaning properties of the adhesive layer formed using the adhesive composition, 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 Tricyclodecanedimethanol diacrylate (curing monomer: manufactured by Shin-Nakamura Chemical Co., Ltd., "A-DCP (brand name)") was dissolved in 280 parts by weight of decahydronaphthalene to prepare the main body of the adhesive composition. Subsequently, as a curing agent, dialkyl peroxide (thermal polymerization initiator: Nippon Oil Co., Ltd. make, "Percumyl D (brand name)") is acetic acid so that the blending amount with respect to 20 parts by weight of tricyclodecane dimethanol diacrylate is 0.4 parts by weight. It was dissolved in 20 parts by weight of butyl. Thereafter, an adhesive composition was prepared by blending the curing agent in the main body.

Subsequently, the adhesive composition of Example 1 was applied to a glass support (glass support, 8 inches, 700 μm in thickness) by a spin coating method, and baked at 90° C. and 140° C. for 5 minutes to be included in the adhesive layer. The used solvent was removed. Subsequently, the cured monomer was polymerized by heating the adhesive layer in a nitrogen gas atmosphere at 200° C. for 1 hour. Thereby, the adhesive layer of Example 1 was formed (film thickness 5 micrometers). In addition, under the same conditions, an adhesive layer was formed on the four glass supports, and each was used for evaluation of chemical resistance and cleaning property.

(Evaluation of drug resistance)

The evaluation of drug resistance was performed by immersing a glass support having an adhesive layer formed on each of cyclopentanone, cyclohexanone, and PGMEA at 23° C. for 5 minutes, and thereafter, the laminate for each drug. It evaluated based on the change in weight and the change in appearance. Chemical resistance was evaluated as "○" when no change in weight and appearance was observed, and "x" when a change in weight or appearance (with or without cracks) was observed. Table 1 shows the results.

(Evaluation of cleanliness)

The glass support on which the adhesive layer of Example 1 was formed was rotated under conditions of 1,000 rpm, and p-mentane was supplied as a peeling solution to spin-wash the glass support. The presence or absence of a residue in the glass support after washing was confirmed with a microscope. In addition, if there is a residue, the residue part is scattered and reflected by the high-intensity light emitted from the microscope to the eye and looks white. When a large amount of residue is seen, the cleaning property is evaluated as "x", when almost no residue is seen, the cleaning property is evaluated as "△", and when no residue is seen, the cleaning property is " ○". Table 1 shows the results.

[Examples 2 to 32]

As Examples 2 to 32, in a composition different from Example 1, a base resin, a curing monomer, and a polymerization initiator were blended, 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. The details of the compositions of Examples 2 to 32 and each evaluation result are shown in Tables 1 to 4.

[Comparative Examples 1 and 2]

As Comparative Examples 1 and 2, an adhesive composition not containing a curing monomer and a polymerization initiator was prepared, except that the adhesive layer was not heated under the conditions of 200°C and 1 hour in Example 1. An adhesive layer was formed on the glass support in the same procedure. Moreover, chemical resistance and cleaning property were evaluated under the same conditions as in Example 1. Table 5 shows the details of the composition of Comparative Example 1 and Comparative Example 2 and each evaluation result.

In addition, the base polymer, curing monomer, and initiator 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 general formula (9): SEPS (Kuraray, "Septon 2002 (brand name)", styrene content 30%, molecular weight 53000)

Styrene-isoprene-styrene triblock copolymer represented by the following general formula (9): SEPS (Kurare Corporation make, "Septon 2004 (brand name)", styrene content 18%, molecular weight 90000)

[Formula 8]

[Cured monomer]

Tricyclodecanedimethanol diacrylate represented by the following formula (10) (manufactured by Shin-Nakamura Chemical Co., Ltd., ``A-DCP (trade name)'')

・Tricyclodecanedimethanoldimethacrylate represented by the following formula (11) (manufactured by Shin-Nakamura Chemical Co., Ltd., ``DCP (brand name)'')

[Formula 9]

[Formula 10]

[Initiator]

Dialkyl peroxide (1 minute half-time temperature/175.2° C., 1 hour half-time temperature/135.7° C., theoretical active oxygen content/5.92%: Nippon Oil Co., Ltd. product, “Percumyl D (brand name)”)

Peroxyester (1 minute half temperature/124.3° C., 1 hour half temperature/84.4° C., theoretical active oxygen content/5.87%: Nippon Oil Co., Ltd. product, “Perocta O (brand name)”)

(Each evaluation result)

As shown in Tables 1 to 5, all of the adhesive layers of Examples 1 to 32 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 that did not contain a curing monomer had good drug resistance against PGMEA, but low drug resistance against cyclopentanone and cyclohexanone (×). From these results, it was confirmed that on the glass support on which the adhesive layer of Examples 1 to 32 was formed, a photolithography process was performed and a wiring layer could be formed.

In addition, 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 are not only chemical resistance , p-mentane was also excellent in cleaning properties (○). Therefore, it was confirmed that by increasing the content of the base polymer to more than 80% by weight and reducing the content of the curing monomer to less than 20% by weight, it was possible to form an adhesive layer having not only high chemical resistance but also high cleaning properties.

<Test for measuring dynamic complex elastic modulus of adhesive layer>

About the adhesive layer composition of Examples 2 and 6 mentioned above, and the adhesive composition of Comparative Examples 1 and 2, the dynamic complex elastic modulus (E*) in the adhesive layer formed by each was measured.

The adhesive composition of Example 2 was adjusted so as to have a solid content concentration of 25% or more, spin-coated on a 6-inch Si wafer, and baked at 90°C and 140°C for 5 minutes each, and under a nitrogen atmosphere at 200°C for 1 hour Treatment to form a 50 µm adhesive layer (film). The film was cut out to a size of 20 mm (measured width is adjusted to 10 mm) x 5 mm to obtain a test piece. The dynamic complex elastic modulus (E*), using a dynamic viscoelasticity measuring device Rheologel-E4000 (manufactured by UBM Co., Ltd.), increases the temperature from 50°C to 250°C at a heating rate of 5°C/min under conditions of a frequency of 1 Hz While making the measurement. Table 9 shows the results. In addition, about the adhesive layer using the adhesive composition of Example 6, Comparative Example 1, and Comparative Example 2, the dynamic complex elastic modulus was measured under the same conditions as the adhesive composition of Example 2. The measurement results are shown in Table 6 below.

As shown in Table 6, for Examples 2 and 6, it was confirmed that a high dynamic complex elastic modulus can be maintained at a high temperature of 250°C. On the other hand, in the adhesive layer formed using the adhesive composition of Comparative Examples 1 and 2, at a high temperature of 200°C or higher, the sample was remarkably softened, and the dynamic complex elastic modulus could not be accurately measured. Accordingly, it was confirmed that the adhesive layer obtained by curing the curing monomer can prevent deformation even when pressure is applied in a high-temperature environment of 200°C or higher compared to the adhesive layer to which the curing monomer is not added. .

<Evaluation of the base polymer contained in the adhesive layer>

The adhesive composition of Comparative Example 3 in which S2004, which is the base polymer in Comparative Example 2, was substituted with a cycloolefin polymer, and the adhesive composition of Comparative Example 4, in which S2004, which is the base polymer in Example 22, was substituted with a cycloolefin polymer. Prepared. Further, the adhesive layer of Comparative Example 4 was formed in the same procedure as in Example 22, and the adhesive layer of Comparative Example 3 was formed in the same procedure as in Comparative Example 2. Then, the dynamic complex elastic modulus (E*) in the adhesive layer of Example 22 and Comparative Examples 2-4 was measured. Moreover, about the adhesive composition of Comparative Example 2 and the adhesive composition of Comparative Example 3, the dissolution rate in the adhesive layer formed by each was measured.

The composition of the adhesive composition of Comparative Examples 3 and 4 is shown in Table 7. In addition, as the base polymer of Comparative Examples 3 and 4, a cycloolefin polymer represented by the following general formula (12): manufactured by Mitsui Chemicals, "APL8008T (brand name)" (the following general formula (12), Mw = 100,000, Mw/ Mn = 2.1, m:n = 80:20 (molar ratio)) was used.

[Formula 11]

(Test for measuring dynamic complex elastic modulus of adhesive layer)

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

As shown in Table 8, when comparing the dynamic complex elastic modulus in the adhesive layers of Example 22 and Comparative Example 4, under the condition of 50°C, the adhesive layer of Comparative Example 4 exhibited a higher dynamic complex elastic modulus, but higher Under the condition of 150°C, which is a temperature, the adhesive layer of Example 22 exhibited a higher dynamic complex elastic modulus. From this, it was confirmed that the adhesive layer of Example 22 was able to maintain a high dynamic complex elastic modulus even under a higher temperature condition. In addition, even when comparing the dynamic complex elastic modulus of the adhesive layer in Comparative Example 2 and Comparative Example 3, the adhesive layer of Comparative Example 2 using a block copolymer maintains a higher dynamic complex elastic modulus at a higher temperature. For this reason, it was confirmed that the use of the block copolymer as the base polymer for the adhesive composition could maintain a high dynamic complex elastic modulus in a high temperature range.

(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 of 5 μm). The support on which the adhesive layer was formed was immersed in p-mentane maintained 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, in Comparative Example 2 in which the block copolymer was used as the base polymer, the dissolution rate was faster than in Comparative Example 3 in which the cycloolefin-based 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 particularly suitably used in the manufacture of a semiconductor device by a fan-out technique.

1: support
3: adhesive layer
4: wiring layer
5: element
6: Encapsulant
7, 7': encapsulant
8, 8', 9, 9': laminate

Claims (20)

In a laminate comprising a wiring layer on which an element is mounted, and an encapsulant comprising an encapsulant that encapsulates the element and the element on a support supporting the encapsulant through an adhesive layer, Of, as an adhesive composition for forming the adhesive layer,
The adhesive composition,
A block copolymer,
A polymerizable monomer,
It contains a polymerization initiator,
The block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof, and an adhesive composition comprising a styrene block. The method of claim 1,
The adhesive composition, wherein the block copolymer is a triblock copolymer having styrene blocks at both ends. The method of claim 1,
An adhesive composition, wherein the amount of the polymerizable monomer is in a range of 1% by weight or more and 50% by weight or less with respect to the total amount of the block copolymer and the polymerizable monomer. The method of claim 1,
The adhesive composition, wherein the block copolymer has a styrene block content of 10% by weight or more and 65% by weight or less. The method of claim 1,
Adhesive composition, characterized in that the weight average molecular weight of the block copolymer is 50,000 or more and 150,000 or less. The method of claim 1,
The adhesive composition, wherein the polymerizable monomer is a (meth)acrylic acid ester. The method of claim 6,
The (meth)acrylic acid ester is an adhesive composition characterized in that it is a polyfunctional (meth)acrylic acid ester. The method of claim 1,
The said polymerization initiator is a thermal polymerization initiator or a photoinitiator, The adhesive composition characterized by the above-mentioned. A laminate comprising a wiring layer on which an element is mounted, and an encapsulant including the element and an encapsulant for encapsulating the element, on a support supporting the encapsulant through an adhesive layer,
The adhesive layer,
A block copolymer,
A polymer of a polymerizable monomer, and
A laminate comprising a polymerization initiator. The method of claim 9,
The block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof, and has a styrene block. The method of claim 10,
The layered product, wherein the block copolymer is a triblock copolymer having styrene blocks at both ends. The method according to any one of claims 9 to 11,
A layered product, wherein 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 a range of 1% by weight or more and 50% by weight or less. The method of claim 10 or 11,
The layered product, wherein the block copolymer has a styrene block content of 10% by weight or more and 65% by weight or less. The method according to any one of claims 9 to 11,
The weight average molecular weight of the block copolymer is 50,000 or more and 150,000 or less. The method according to any one of claims 9 to 11,
The layered product, wherein the polymer of the polymerizable monomer is a polymer of (meth)acrylic acid ester. The method of claim 15,
The (meth)acrylic acid ester polymer is a multifunctional (meth)acrylic acid ester polymer. A method for manufacturing a laminate comprising a wiring layer on which an element is mounted, and an encapsulant comprising the element and an encapsulant for encapsulating the element, which is laminated on a support for supporting the encapsulant via an adhesive layer, comprising:
A method for producing a laminate, comprising a step of forming an adhesive layer by applying the adhesive composition according to any one of claims 1 to 8 on the support. A method for manufacturing a laminate comprising a wiring layer on which an element is mounted, and an encapsulant comprising the element and an encapsulant for encapsulating the element, which is laminated on a support for supporting the encapsulant via an adhesive layer, comprising:
A method for producing a laminate, comprising a step of forming the adhesive layer by applying the adhesive composition according to claim 8 on the support and heating or exposing it to light. By the method for producing a laminate according to claim 17, a laminate manufacturing process for producing a laminate is included,
In the above laminate, the support is a support that transmits light, and a separation layer that is deteriorated by absorbing light is formed between the support and the adhesive layer,
After the laminate manufacturing process, by irradiating light to the separating layer through the support to denature the separating layer, a separating step of separating the support from the laminate,
And a washing step of removing the adhesive layer remaining on the side of the sealing member with a hydrocarbon-based solvent. delete

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