JP7004566B2 - Laminates and their manufacturing methods, as well as electronic component manufacturing methods - Google Patents

Description

The present invention relates to a laminate, a method for manufacturing the same, and a method for manufacturing electronic components.

A semiconductor package (electronic component) including a semiconductor element has various forms depending on the corresponding size, and includes, for example, WLP (Wafer Level Package), PLP (Panel Level Package), and the like.
Examples of the semiconductor package technology include fan-in type technology and fan-out type technology. As a semiconductor package by fan-in type technology, a fan-in type WLP (Fan-in Wafer Level Package) or the like in which terminals at the end of a bare chip are rearranged in a chip area is known. As a semiconductor package based on the fan-out type technology, a fan-out type WLP (Fan-out Wafer Level Package) or the like in which the terminals are rearranged outside the chip area is known.

In recent years, in particular, fan-out type technology has been applied to fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged and packaged on a panel. It is attracting attention as a method that can realize thinning and miniaturization.

In order to reduce the size of the semiconductor package, it is important to reduce the thickness of the substrate in the element to be incorporated. However, if the thickness of the substrate is reduced, the strength thereof is reduced, and the substrate is liable to be damaged during the manufacture of the semiconductor package. On the other hand, a laminated body in which a support is bonded to a substrate is adopted.

Here, when the substrate and the support are bonded to each other, an adhesive containing a polymer having a cycloolefin structure has been widely used because of its excellent light transmittance.
Patent Document 1 discloses an adhesive composition containing a polymer having a cycloolefin structure and a (meth) acrylate monomer compatible with the polymer.

Japanese Unexamined Patent Publication No. 2014-105316

By the way, in the fan-out type technology, a substrate sealed with a molding material is used as the substrate arranged on the support, or a structure in which an insulating resin and a metal wiring are combined is provided on the support. Sometimes. For example, as such a molding material, a resin material such as a hygroscopic epoxy resin is used. In semiconductor package manufacturing, after sealing with a sealing material, high temperature treatment such as thin film formation and firing is performed. At that time, the moisture in the resin contained in the encapsulant evaporates to generate gas, and voids (foam) are generated between the substrate and the support, which causes problems such as peeling of the support. There is a concern that it will arise.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminated body capable of reducing the risk of peeling between the device layer and the support even when subjected to high temperature treatment.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is a laminated body in which a support, an adhesive layer, an intermediate layer and a device layer are laminated in this order, and at least the intermediate layer and the device layer are adjacent to each other. The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member, and the intermediate layer has a thickness of 20 μm at a temperature of 40 ° C. and a humidity of 90% RH. It is a laminate made of a material that satisfies the requirement that the converted water vapor permeability is 5 g / (m ² · day) or less.

A second aspect of the present invention is a laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order, and at least the intermediate layer and the device layer are adjacent to each other, and the device. The layer is a composite of a member made of metal or semiconductor and a resin that seals or insulates the member, and the intermediate layer prepares a test piece having a thickness of 500 μm, and starts at a starting temperature of 25 ° C. and rises. It is composed of a material that meets the requirements that the melt viscosity at 180 ° C is 10,000 (Pa · s) or more when subjected to dynamic viscoelasticity measurement under the conditions of temperature rate: 5 ° C / min and frequency: 1 Hz. It is a laminated body.

A third aspect of the present invention is a laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order, and at least the intermediate layer and the device layer are adjacent to each other, and the device. The layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member, and the intermediate layer is a laminate containing a cycloolefin polymer.

A fourth aspect of the present invention is a method for producing a laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order, and an adhesive layer is formed on the support using an adhesive composition. Adhesive layer forming step to form a device layer, which is a composite of a member composed of a metal or a semiconductor and a resin that seals or insulates the member, and a device layer forming step on the device layer or the above. An intermediate layer forming step of forming an intermediate layer on the adhesive layer using an intermediate layer forming material, and device layer fixing for fixing the device layer on the support via the adhesive layer and the intermediate layer. Including the step, the intermediate layer forming material is a material that satisfies the requirement that the water vapor permeability in terms of thickness 20 μm is 5 g / (m ² · day) or less at a temperature of 40 ° C. and a humidity of 90% RH. There is a method for manufacturing a laminated body.

A fifth aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer, an intermediate layer and a device layer are laminated in this order, and an adhesive layer is formed on the support using an adhesive composition. Adhesive layer forming step to form a device layer, which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member, and a device layer forming step on the device layer or the above. An intermediate layer forming step of forming an intermediate layer on the adhesive layer using an intermediate layer forming material, and device layer fixing for fixing the device layer on the support via the adhesive layer and the intermediate layer. Including the step, the intermediate layer forming material prepares a test piece having a thickness of 500 μm, and is used for dynamic viscous elasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz. It is a method for producing a laminated body, which is a material that satisfies the requirement that the melt viscosity is 10,000 (Pa · s) or more at 180 ° C. when attached.

A sixth aspect of the present invention is a method for producing a laminated body in which a support, an adhesive layer, an intermediate layer and a device layer are laminated in this order, and an adhesive layer is formed on the support using an adhesive composition. Adhesive layer forming step to form a device layer, which is a composite of a member composed of a metal or a semiconductor and a resin that seals or insulates the member, and a device layer forming step on the device layer or the above. An intermediate layer forming step of forming an intermediate layer on the adhesive layer using an intermediate layer forming material, and device layer fixing for fixing the device layer on the support via the adhesive layer and the intermediate layer. A method for producing a laminate, which comprises a step and the intermediate layer forming material is a material containing a cycloolefin polymer.

A seventh aspect of the present invention is to obtain a laminate by the method for producing a laminate according to any one of the fourth to sixth aspects, and then irradiate the separation layer with light via the support substrate. By altering the separation layer, the separation step of separating the support substrate from the device layer provided in the laminate, and removal of the adhesive layer and the intermediate layer adhering to the device layer after the separation step. It is a manufacturing method of an electronic part including a process.

According to the present invention, it is an object of the present invention to provide a laminate capable of reducing the risk of peeling between the device layer and the support even when subjected to high temperature treatment.

It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic process diagram explaining one Embodiment of the manufacturing method of the support 123 with an adhesive layer composed of a support and an adhesive layer. FIG. 5A is a diagram showing a support substrate composed of a support substrate and a separation layer, and FIG. 5B is a diagram illustrating an adhesive layer forming step. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a laminated body 100 from a support 123 with an adhesive layer. FIG. 6A is a diagram showing a support 123 with an adhesive layer, FIG. 6B is a diagram showing an intermediate layer forming step, and FIG. 6C is a diagram illustrating a device layer fixing step. It is a figure. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a laminated body 200 from a laminated body 100. 7 (a) is a diagram showing the laminated body 100, FIG. 7 (b) is a diagram for explaining a grinding process, and FIG. 5 (c) is a diagram for explaining a wiring layer forming process. It is a schematic process diagram explaining one Embodiment of the method of manufacturing a semiconductor package (electronic component) from a laminated body 200. 8 (a) is a diagram showing the laminated body 200, FIG. 8 (b) is a diagram for explaining a separation step, and FIG. 8 (c) is a diagram for explaining a removal step. It is a graph which measured the amount of gas released from the mold material containing an epoxy resin. FIG. 9A is a graph showing the total amount of gas released, and FIG. 9B is a graph showing the amount of water vapor released.

In the present specification and claims, "aliphatic" is defined as a relative concept to aromatics and means a group, a compound or the like having no aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of the hydrogen atom of the alkyl group or the alkylene group is substituted with a fluorine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described that "may have a substituent" or "may have a substituent", the case where the hydrogen atom (-H) is substituted with a monovalent group and the case where the methylene group (-CH ₂ ) is substituted. Includes both cases where-) is replaced with a divalent group.
"Exposure" is a concept that includes general irradiation of radiation.

The “constituent unit derived from hydroxystyrene” means a structural unit composed by cleavage of the ethylenic double bond of hydroxystyrene. The “constituent unit derived from the hydroxystyrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the hydroxystyrene derivative.
The term "hydroxystyrene derivative" is a concept including a hydrogen atom at the α-position of hydroxystyrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent. The hydrogen atom of the hydroxyl group of hydroxystyrene is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group is bonded to a good hydroxystyrene benzene ring. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of hydroxystyrene include the same as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
Further, as the hydroxyalkyl group as the substituent at the α-position, specifically, a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a hydroxyl group can be mentioned. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, most preferably 1.

(Laminated body (first aspect))
The laminate according to the first aspect of the present invention is a laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order, and at least the intermediate layer and the device layer are adjacent to each other. It is a thing. The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. The intermediate layer is made of a material that satisfies the requirement that the water vapor transmittance in terms of thickness 20 μm is 5 g / (m ² · day) or less at a temperature of 40 ° C. and a humidity of 90% RH.

FIG. 1 shows an embodiment of a laminated body according to the first aspect.
The laminate 100 shown in FIG. 1 includes a support 12 composed of a support substrate 1 and a separation layer 2, an adhesive layer 3, an intermediate layer 10, and a device layer 45 composed of a substrate 4 and a sealing material layer 5. ing. In the laminated body 100, the support 12, the adhesive layer 3, the intermediate layer 10 and the device layer 456 are laminated in this order. In the example of FIG. 1, the support 12 is composed of the support base 1 and the separation layer 2, but the support is not limited to this, and the support may be formed only from the support base.
The intermediate layer 10 is provided adjacent to the device layer 45, so that even if the gas is released from the device layer 45 during the heat treatment, it is possible to prevent the gas from spreading to the adhesive layer 3 side. ..

FIG. 2 shows another embodiment of the laminate according to the first aspect.
The laminate 200 shown in FIG. 2 has the same configuration as the laminate 100 except that the device layer is the device layer 456 composed of the substrate 4, the encapsulant layer 5, and the wiring layer 6.

FIG. 3 shows yet another embodiment of the laminate according to the first aspect.
The laminated body 300 shown in FIG. 3 has the same configuration as the laminated body 100 except that the device layer is composed of the wiring layer 6.

FIG. 4 shows yet another embodiment of the laminate according to the first aspect.
The laminate 400 shown in FIG. 4 has the same configuration as the laminate 100 except that the device layer is the device layer 645 including the wiring layer 6, the substrate 4, and the encapsulant layer 5.

<Middle layer>
The intermediate layer is a layer provided adjacent to the device layer between the adhesive layer and the device layer, and is composed of an intermediate layer forming material. The intermediate layer has a function of suppressing the release of gas from the device layer.

In the present embodiment, the intermediate layer forming material satisfies the following (requirement 1-1).
(Requirement 1-1): At a temperature of 40 ° C. and a humidity of 90% RH, the water vapor permeability in terms of a thickness of 20 μm is 5 g / (m ² · day) or less.

The measurement of the water vapor permeability in the above (Requirement 1-1) can be performed in accordance with JIS K7129B.

By providing an intermediate layer made of a material satisfying the above (Requirement 1-1) adjacent to the device layer, it is possible to effectively suppress the release of gas from the device layer. The water vapor permeability in the above (requirement 1-1) is preferably 3 g / (m ² · day) or less, and more preferably 1 g / (m ² · day) or less. The lower limit of the water vapor transmittance is not particularly limited, but is, for example, 0.01 g / (m ² · day) or more.

As the intermediate layer forming material, any known material can be used without particular limitation as long as it satisfies the above (Requirement 1-1) and can form a film. Examples of such materials include cycloolefin polymers, inorganic substances, various resin materials used as packaging film materials, and the like.

≪Cycloolefin polymer≫
Preferable examples of the cycloolefin polymer include a ring-opening polymer having a monomer component containing a cycloolefin monomer and an addition polymer obtained by addition-polymerizing a monomer component containing a cycloolefin monomer.

Examples of the cycloolefin monomer include dicyclics such as norbornene and norbornadiene, tricyclics such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclics such as tetracyclopentadiene, and cyclopentadiene trimers. Rings, seven rings such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substitutions, alkenyl (vinyl, etc.) substitutions, alkylidene (ethylidene, etc.) substitutions or aryls (such as ethylidene) of these polycyclics. Monomers such as phenyl, trill, naphthyl, etc.) substituents can be mentioned.

Among the above, a polymer having a structural unit derived from a monomer having a norbornene structure, which is selected from the group consisting of norbornene, tetracyclododecene and alkyl-substituted products thereof, is particularly preferable. By using such a cycloolefin polymer having a norbornene structure, the water vapor permeability can be reduced.

The cycloolefin polymer may have a monomer copolymerizable with the cycloolefin monomer as a monomer unit.
As such a copolymerizable monomer, for example, an alkene monomer is preferably mentioned. The alkene monomer may be linear or branched, and examples thereof include alkene monomers having 2 to 10 carbon atoms, and examples thereof include ethylene, propylene, 1-butene, isobutene, and 1. -Α-olefins such as hexene are preferable, and among these, ethylene is more preferable as a monomer unit.

The content ratio of the cycloolefin monomer unit in the cycloolefin polymer is preferably 30 mol% or more, more preferably 40 mol% or more, based on the total constituent units (100 mol%) constituting the cycloolefin polymer. When the content ratio of the cycloolefin monomer unit is at least the lower limit of the above preferable range, the water vapor transmittance can be reduced. The upper limit of the content ratio of the cycloolefin monomer unit is not particularly limited, but is, for example, 90 mol% or less with respect to all the constituent units (100 mol%) constituting the cycloolefin polymer.

As the cycloolefin polymer, one type may be used alone, or two or more types may be used in combination.

The cycloolefin polymer is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, which is a gas at a high temperature. It is preferable from the viewpoint of suppressing the occurrence of.
The polymerization method, polymerization conditions, etc. when polymerizing the monomer component are not particularly limited and may be appropriately set according to a conventional method.

Commercially available cycloolefin polymers include, for example, "TOPAS (trade name)" manufactured by Polyplastics Corporation, "APEL (trade name)" manufactured by Mitsui Kagaku Co., Ltd., and "ZEONOR (trade name)" manufactured by Japan Zeon Co., Ltd. Name) ”,“ ZEONEX (trade name) ”manufactured by Japan Zeon Co., Ltd.,“ ARTON (trade name) ”manufactured by JSR Corporation, and the like.

The cycloolefin polymer may be used in the intermediate layer as a cycloolefin polymer composition by adding other components as appropriate. Examples of such other components include diluting solvents, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants and the like. As these, known ones can be used without particular limitation. Examples of the diluting solvent include those mentioned in "<< Adhesive layer >>" described later.

≪Inorganic matter≫
The inorganic substance as the intermediate layer forming material is not particularly limited as long as it satisfies the above (requirement 1-1). As such an inorganic substance, for example, one or more kinds selected from the group consisting of a metal, a metal compound and carbon are preferably mentioned. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.
Examples of such an inorganic substance include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si _{3N 4 ,} TiN, and carbon. Here, carbon is a concept that can also include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.

The intermediate layer made of an inorganic film can be formed on the adhesive layer by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like.

≪Various resin materials≫
The resin material that can be used as the intermediate layer forming material is not particularly limited, and for example, a known resin material or the like as a packaging film material can be used as long as it is a material that satisfies the above (requirement 1-1). Examples of such resin materials include, but are not limited to, the resin materials shown in Table 1 below.

Each abbreviation in Table 1 is as follows.
PET: Polyethylene terephthalate CPP: Unstretched polypropylene ONY: Nylon PVDC: Polyvinylidene chloride VDC: Vinyl chloride MA: Methacrylate OPP: Biaxially stretched polypropylene PVC: Polyvinyl chloride

The intermediate layer forming material preferably satisfies the following (requirement 1-2) in addition to the above (requirement 1-1).
(Requirement 1-2): When a test piece having a thickness of 500 μm was prepared and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz, 180. The melt viscosity at ° C. is 10,000 (Pa · s) or more.

The measurement of the melt viscosity in the above (requirement 1-2) is carried out using a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM Co., Ltd.) in accordance with the conditions described in the above (requirement 1-2). can do.

By satisfying (Requirement 1-2) in addition to the above (Requirement 1-1), outgassing from the device layer can be suppressed more effectively. The melt viscosity in the above (Requirement 1-2) is preferably 15,000 (Pa · s) or more, more preferably 20000 (Pa · s) or more, and even more preferably 25,000 (Pa · s) or more. The upper limit of the melt viscosity is not particularly limited, but is, for example, 50,000 (Pa · s) or less.

The thickness of the intermediate layer is, for example, preferably in the range of 0.1 μm or more and 50 μm or less, more preferably in the range of 5 μm or more and 40 μm or less, and more preferably in the range of 10 μm or more and 30 μm or less. Is more preferable, and it is particularly preferable that the range is 15 μm or more and 25 μm or less.
When the thickness of the intermediate layer is at least the lower limit of the preferable range, the function of blocking the gas released from the device layer is improved. Further, when the thickness of the intermediate layer is not more than the upper limit of the preferable range, it does not interfere with the subsequent removal step.

<Adhesive layer>
The adhesive layer is a layer for adhering the support and the substrate, and can be formed by using the adhesive composition described later.

The thickness of the adhesive layer is, for example, preferably 0.1 μm or more and 100 μm or less, more preferably 1 μm or more and 50 μm or less, and 10 μm or more and 40 μm or less. Is even more preferable. When the thickness of the adhesive layer is within the above-mentioned preferable range, the support and the substrate can be better bonded to each other.

The ratio of the thickness (μm) of the adhesive layer to the thickness (μm) of the intermediate layer is preferably the adhesive layer / intermediate layer = 1/9 to 9/1. When the ratio is within the preferable range, it is possible to suppress the release of gas from the device layer while maintaining the adhesiveness between the support and the substrate. The ratio is more preferably 1/5 to 5/1 for the adhesive layer / intermediate layer, and further preferably 1/1 to 4/1 for the adhesive layer / intermediate layer.

≪Adhesive composition≫

The adhesive composition preferably satisfies the following (requirement A).
(Requirement A): When a test piece having a thickness of 500 μm was prepared and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz, the temperature was 180 ° C. The melt viscosity of is 1000 (Pa · s) or more and 10000 (Pa · s) or less.

The measurement of the melt viscosity in the above (requirement A) can be performed according to the same procedure as the measurement of the melt viscosity in (requirement 1-2) in the above "<intermediate layer>".

When the adhesive composition satisfies (Requirement A), the adhesive composition tends to exhibit a stable adhesive function at both normal temperature and heating. The melt viscosity in the above (requirement A) is more preferably 2000 (Pa · s) or more and 8000 (Pa · s) or less, and further preferably 2000 (Pa · s) or more and 6000 (Pa · s) or less.

As the adhesive composition, various adhesive compositions known in the art such as acrylic type, novolak type, naphthoquinone type, hydrocarbon type, polyimide type, elastomer, polysulfone type and the like can be used.

Examples of the adhesive composition include those containing other components such as a thermoplastic resin, a diluent, and an additive. The thermoplastic resin may be any one that exhibits adhesive strength, and for example, a hydrocarbon resin, an acrylic-styrene resin, a maleimide resin, an elastomer resin, a polysulfone resin, or a combination thereof is preferable. Can be used.

-Hydrocarbon resin A hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerized with a monomer composition. As the hydrocarbon resin, at least one resin selected from the group consisting of a cycloolefin polymer (hereinafter, may be referred to as "resin (A)"), a terpene resin, a rosin-based resin, and a petroleum resin (hereinafter, "" It may be referred to as “resin (B)”), etc., but is not limited thereto.

Preferred examples of the resin (A) include a ring-opening polymer having a monomer component containing a cycloolefin monomer and an addition polymer obtained by addition-polymerizing a monomer component containing a cycloolefin monomer.

Examples of the cycloolefin monomer include those similar to those mentioned in the above "<intermediate layer>".
The cycloolefin polymer may have a monomer copolymerizable with the cycloolefin monomer as a monomer unit, and the copolymerizable monomer is also the same as that mentioned in the above "<intermediate layer>". Can be mentioned.

Further, it is preferable to contain a cycloolefin monomer as a monomer component constituting the resin (A) from the viewpoint of high heat resistance (low thermal decomposition, thermal weight reduction). The ratio of the cycloolefin monomer to the total monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. The ratio of the cycloolefin monomer to the entire monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution. It is more preferably 70 mol% or less.

Further, as a monomer component constituting the resin (A), a linear or branched alkene monomer may be contained. The ratio of the alkene monomer to the total monomer component constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. , 30-80 mol%, more preferably.

The resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, at a high temperature. It is preferable for suppressing the generation of gas.
The polymerization method, polymerization conditions, etc. when polymerizing the monomer component are not particularly limited and may be appropriately set according to a conventional method.

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

The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition temperature of the resin (A) is 60 ° C. or higher, softening of the adhesive layer can be suppressed when exposed to a high temperature environment.

The resin (B) is at least one resin selected from the group consisting of a terpene-based resin, a rosin-based resin, and a petroleum resin. Specifically, examples of the terpene-based resin include terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin and the like. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, modified rosin and the like. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and Kumaron-Inden petroleum resins. Among these, hydrogenated terpene resin and hydrogenated petroleum resin are more preferable.

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 ° C. When the softening point of the resin (B) is 80 to 160 ° C., softening can be suppressed when exposed to a high temperature environment, and poor adhesion does not occur.

The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance becomes sufficient and the amount of degassing becomes small in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the dissolution rate of the adhesive layer in the hydrocarbon solvent becomes good. Therefore, the residue of the adhesive layer on the device layer after the support is separated can be quickly dissolved and removed. The weight average molecular weight of the resin (B) in the present embodiment means the polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).

As the hydrocarbon resin, a mixture of the resin (A) and the resin (B) may be used. By mixing, the heat resistance becomes good. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio), that is, the heat resistance in a high temperature environment and the heat resistance. It is preferable because it has excellent flexibility.

-Acrylic-styrene resin Examples of the acrylic-styrene resin include a resin obtained by polymerizing a styrene or a derivative of styrene and a (meth) acrylic acid ester or the like as a monomer.

Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. .. Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms, and the like. .. As the acrylic long chain alkyl ester, acrylic acid or methacrylic acid whose alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group or the like Alkyl esters can be mentioned. The alkyl group may be in the form of a branched chain.

Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives. For example, the alkyl group is an alkyl of acrylic acid or methacrylic acid consisting of a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group, an isodecyl group, a dodecyl group, a lauryl group, a tridecyl group and the like. Esther can be mentioned.

Examples of the (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl. Examples thereof include (meth) acrylate, tetracyclododecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate, but isobornyl methacrylate and dicyclopentanyl (meth) acrylate are more preferable.

The (meth) acrylic acid ester having an aromatic ring is not particularly limited, but the aromatic ring includes, for example, a phenyl group, a benzyl group, a tolyl group, a xsilyl group, a biphenyl group, a naphthyl group and an anthrasenyl group. , Phenoxymethyl group, phenoxyethyl group and the like. Further, the aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

-Maleimide-based resin Examples of the maleimide-based resin include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, and N-isobutylmaleimide as monomers. , N-sec-butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N -Alipid hydrocarbons such as maleimide having an alkyl group such as stearylmaleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide and N-cyclooctylmaleimide. It was obtained by polymerizing aromatic maleimide having an aryl group such as maleimide having a group, N-phenylmaleimide, Nm-methylphenylmaleimide, NO-methylphenylmaleimide, Np-methylphenylmaleimide and the like. Resin is mentioned.

-Elastomer The elastomer preferably contains a styrene unit as a constituent unit of the main chain, and the "styrene unit" may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, a carboxyl group and the like. Further, it is more preferable that the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less. Further, the elastomer preferably has a weight average molecular weight in the range of 10,000 or more and 200,000 or less.

If the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, the hydrocarbon solvent described later will be used. Since it dissolves easily, the adhesive layer can be removed more easily and quickly. Further, when the content of the styrene unit and the weight average molecular weight are within the above ranges, the resist solvent (for example, PGMEA, PGME, etc.), acid (hydrofluoric acid, etc.), alkali (TMAH, etc.) used for resist lithography are used. Exhibits excellent resistance to.

The above-mentioned (meth) acrylic acid ester may be further mixed with the elastomer.

The content of the styrene unit is more preferably 17% by weight or more, and more preferably 40% by weight or less.

A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

As the elastomer, various elastomers as long as the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less. Can be used. 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 these hydrogenated products, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene- Styrene-styrene block copolymer (SEEPS), styrene block reaction cross-linked styrene-ethylene-ethylene-propylene-styrene block copolymer (SeptonV9461 (manufactured by Kuraray Co., Ltd.), SeptonV9475 (manufactured by Kuraray Co., Ltd.)), styrene block reaction crosslinked Styrene-ethylene-butylene-styrene block copolymer (SeptonV9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene-based hard block), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH) : Terminal hydroxyl group modification) and the like, and those in which the content of the styrene unit and the weight average molecular weight of the elastomer are within the above ranges can be used.

Further, among the elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, its stability against heat is improved, and deterioration such as decomposition and polymerization is unlikely to occur. Further, it is more preferable from the viewpoint of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Further, among the elastomers, those having styrene block polymers at both ends are more preferable. This is because styrene, which has high thermal stability, is blocked at both ends to exhibit higher heat resistance.

More specifically, the elastomer is more preferably hydrogenated from block copolymers of styrene and conjugated diene. Stability against heat is improved, and deterioration such as decomposition and polymerization is unlikely to occur. In addition, it exhibits higher heat resistance by blocking styrene, which has high thermal stability, at both ends. Further, it is more preferable from the viewpoint of solubility in a hydrocarbon solvent and resistance to a resist solvent.

Commercially available products that can be used as elastomers contained in adhesive compositions include, for example, "Septon (trade name)" manufactured by Kuraray Corporation, "Hyblur (trade name)" manufactured by Kuraray Corporation, and "Tough Tech" manufactured by Asahi Kasei Corporation. Product name) ”,“ Dynalon (product name) ”manufactured by JSR Corporation, and the like.

The content of the elastomer contained in the adhesive composition is, for example, preferably in the range of 50 parts by weight or more and 99 parts by weight or less, with the total amount of the adhesive composition being 100 parts by weight, and 60 parts by weight or more and 99 parts by weight. The following range is more preferable, and the range of 70 parts by weight or more and 95 parts by weight or less is most preferable. By keeping the temperature within these ranges, the substrate can be suitably fixed to the support while maintaining heat resistance.

Further, a plurality of types of elastomers may be mixed. That is, the adhesive composition may contain a plurality of types of elastomers. Then, at least one of the plurality of types of elastomers may contain a styrene unit as a constituent unit of the main chain. Further, at least one of the plurality of types of elastomer has a styrene unit content in the range of 14% by weight or more and 50% by weight or less, or a weight average molecular weight of 10,000 or more and 200,000 or less. If it is within the range, it is within the scope of the present invention. Further, when the adhesive composition contains a plurality of types of elastomers, the content of the styrene unit may be adjusted to be within the above range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight are combined in a weight ratio of 1. When mixed 1: 1 the styrene content to the total elastomer contained in the adhesive is 21-22% by weight, and thus 14% by weight or more. Further, for example, when a styrene unit having a styrene unit of 10% by weight and a styrene unit having a weight ratio of 60% by weight is mixed at a weight ratio of 1: 1, it becomes 35% by weight, which is within the above range. The present invention may have such a form. Further, it is most preferable that all of the plurality of types of elastomers contained in the adhesive composition contain styrene units within the above range and have a weight average molecular weight within the above range.

-Polysulfone-based resin The adhesive composition may contain polysulfone-based resin. By forming the adhesive layer 3 with polysulfone-based resin, even if high-temperature treatment is performed in the encapsulant forming step, the adhesive layer 3 is melted in the subsequent steps and the support substrate 1 is peeled off from the encapsulant 7. Can be done. If the adhesive layer 3 contains the polysulfone resin, a high temperature process of treating at a high temperature of, for example, 300 ° C. or higher can be used in the sealing body forming step.

The polysulfone-based resin has a structure composed of a structural unit represented by the following general formula (ad1) and at least one of the structural units represented by the following general formula (ad2).

［式中、Ｒ^Ｃ３、Ｒ^Ｃ４、Ｒ^Ｃ５、Ｒ^Ｃ３及びＲ^Ｃ４は、それぞれ独立して、フェニレン基、ナフチレン基及びアントリレン基からなる群より選択される基であり、Ｘ’は、炭素数１～３のアルキレン基である。］

[In the formula, ^RC3 , ^RC4 , ^RC5 , RC3 and ^RC4 are independently selected from the group consisting of a phenylene group, a naphthylene group and an anthrylene group, and ^X'is the number of carbon atoms. It is 1 to 3 alkylene groups. ]

The polysulfone-based resin comprises at least one of the polysulfone structural unit represented by the formula (ad1) and the polyethersulfone structural unit represented by the formula (ad2), whereby the adhesive layer is formed on the support. It is possible to prevent the adhesive layer from being insolubilized due to decomposition, polymerization, or the like, even if the treatment under high temperature conditions is performed after the formation of the layer. Further, the polysulfone-based resin is stable even when heated to a higher temperature as long as it is a polysulfone resin composed of the polysulfone structural unit represented by the above formula (ad1).

The weight average molecular weight (Mw) of the polysulfone-based resin is preferably in the range of 30,000 or more and 70,000 or less, and more preferably in the range of 30,000 or more and 50,000 or less. When the weight average molecular weight (Mw) of the polysulfone-based resin is in the range of 30,000 or more, an adhesive composition that can be used at a high temperature of, for example, 300 ° C. or higher can be obtained. Further, if the weight average molecular weight (Mw) of the polysulfone-based resin is within the range of 70,000 or less, it can be suitably dissolved by a solvent. That is, it is possible to obtain an adhesive composition that can be suitably removed by a solvent.

-Diluting solvent Examples of the diluting solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane, and tridecane, and branched chain carbide having 4 to 15 carbon atoms. Cyclic hydrocarbons such as hydrogen, for example cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, p-menthan, o-menthan, m-menthan, diphenylmentan, 1,4-terpine, 1,8 -Terpine, Bornan, Norbornan, Pinan, Tujan, Karan, Longihoren, Geraniol, Nerol, Linarol, Citral, Citronerol, Mentor, Isomentol, Neomentol, α-Terpineol, β-Terpineol, γ-Terpineol, Terpinen-1-ol , Terpine-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineol, borneol, carboxylic, yonon, tuyon, camphor, d-lymonen, l-lymonen, dipentene and other terpene-based solvents; lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like. Polyhydric alcohols; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ethers and monomethyl ethers of the polyhydric alcohols or compounds having the ester bond. Derivatives of polyhydric alcohols such as monoalkyl ethers such as ethyl ether, monopropyl ether and monobutyl ether or compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol Monomethyl ether (PGME) is preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methoxy Ethers such as methyl propionate and ethyl ethoxypropionate; anisole, ethylbenzyl Examples thereof include aromatic organic solvents such as ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, and butyl phenyl ether.

-Other Ingredients The adhesive composition may further contain other miscible substances as long as the essential properties are not impaired. For example, additional resins, curable monomers, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants, etc. for improving the performance of adhesives are commonly used. Various additives can be further used.

<Support>
The support is a member that supports the substrate, and the substrate is fixed on the support via an adhesive layer. In the examples of FIGS. 1 and 2, the support 12 includes a support base 1 and a separation layer 2 provided on the support base 1. If the separation layer 2 is not provided, the support substrate 1 becomes a support.

≪Supporting substrate≫
The support substrate has the property of transmitting light. The support substrate is a member that supports the substrate, and when a separation layer is provided, it is attached to the substrate via the separation layer and the adhesive layer. When the separation layer is not provided, the support substrate is bonded to the substrate via the adhesive layer. Therefore, it is preferable that the support substrate has the strength necessary to prevent the substrate from being damaged or deformed when the device is thinned, the substrate is transported, or the substrate is mounted on the substrate. Further, the support substrate is preferably one that transmits light having a wavelength that can change the quality of the separation layer.
As the material of the support substrate, for example, glass, silicon, acrylic resin and the like are used. Examples of the shape of the support substrate include, but are not limited to, a rectangle, a circle, and the like.
Further, as the support substrate, in order to further increase the density and improve the production efficiency, it is possible to use a support substrate having a larger size, which is circular, or a large panel having a quadrangular shape in a plan view.

≪Separation layer≫
The separation layer is a layer adjacent to the adhesive layer, which is altered by irradiation with light and enables the support substrate to be separated from the substrate bonded to the support.
This separation layer can be formed by using the composition for forming a separation layer described later, for example, by calcining the components contained in the composition for forming a separation layer, or by a chemical vapor deposition (CVD) method. It is formed. This separation layer is suitably denatured by absorbing the light transmitted through the support substrate and irradiated.
The term "deterioration" of the separation layer means a phenomenon in which the separation layer can be destroyed by an external force or a state in which the adhesive force between the separation layer and the layer in contact with the separation layer is reduced. The separation layer becomes brittle by absorbing light and loses its strength or adhesiveness before being exposed to light. The alteration of the separation layer occurs by causing decomposition by the energy of absorbed light, change in configuration, dissociation of functional groups, and the like.
The separation layer is preferably formed only from a material that absorbs light, but is a layer containing a material that does not have a structure that absorbs light to the extent that the essential properties of the present invention are not impaired. There may be.

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

It is preferable that the surface of the separation layer on the side in contact with the adhesive layer is flat (no unevenness is formed), whereby the adhesive layer can be easily formed and the support substrate and the substrate are uniformly adhered. It will be easy to attach.

[Composition for forming a separation layer]
The composition for forming a separation layer, which is a material for forming a separation layer, is, for example, fluorocarbon, a polymer having a repeating unit including a structure having light absorption, an inorganic substance, or a compound having an infrared absorption structure. , Infrared absorbers, reactive polysilsesquioxane, or those containing a resin component having a phenolic skeleton.
Further, the composition for forming a separation layer improves the separability of a filler, a plasticizer, a thermoacid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a support substrate as optional components. It may contain a possible component or the like.

-The fluorocarbon separation layer may contain fluorocarbon. The separation layer composed of fluorocarbon is adapted to be altered by absorbing light, and as a result, loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support), the separation layer can be broken and the support and the substrate can be easily separated. The fluorocarbon constituting the separation layer can be suitably formed by a plasma CVD method.
Fluorocarbons absorb light with wavelengths in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the fluorocarbon used for the separation layer, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer is preferably 80% or more.

The light to irradiate the separation layer is, for example, a YAG laser, a ruby laser, a glass laser, a _YVO4 laser, an LD laser, a solid laser such as a fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that fluorocarbon can absorb. , CO ₂ laser, excima 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. As the wavelength capable of altering the fluorocarbon, for example, a wavelength in the range of 600 nm or less can be used.

-Polymer having a repeating unit including a structure having a light absorption The separation layer may contain a polymer having a repeating unit including a structure having a light absorption property. The polymer is altered by being irradiated with light.
Examples of the structure having photoabsorbability include 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 having light absorption is a cardo structure, or a benzophenone structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure (bisphenyl sulfone structure), or a diphenyl present in the side chain of the polymer. Structure or diphenylamine structure can be mentioned.
The above-mentioned structure having light absorption ability can absorb light having a wavelength in a desired range depending on the type thereof. For example, the wavelength of light that can be absorbed by the structure having light absorption is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

The light that can be absorbed by the above-mentioned light-absorbing structure is, for example, a high-pressure mercury lamp (wavelength 254 nm or more and 436 nm or less), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ . Light emitted from an Xima laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), XeF laser (wavelength 351 nm) or solid UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line. (Wavelength 365 nm) and the like.

-The inorganic substance separation layer may be made of an inorganic substance. The inorganic substance may be any substance that is altered by absorbing light, and for example, one or more selected from the group consisting of a metal, a metal compound, and carbon is preferably mentioned. The metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides.
Examples of such an inorganic substance include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si _{3N 4 ,} TiN, and carbon.
Note that carbon is a concept that may include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like.
The inorganic substance absorbs light having a wavelength in a unique range depending on the type.

The light irradiating the separation layer made of an inorganic substance may be, for example, a solid laser such as a YAG laser, a ruby laser, a glass laser, a _YVO4 laser, an LD laser, or a fiber laser, or a dye laser, depending on the wavelength that the inorganic substance can absorb. Liquid lasers such as, CO ₂ lasers, excima lasers, Ar lasers, gas lasers such as He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, or non-laser light may be appropriately used.
The separation layer made of an inorganic substance can be formed on a support substrate by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

-The compound having an infrared absorbing structure The separation layer may contain a compound having an infrared absorbing structure. This compound having an infrared absorbing structure is altered by absorbing infrared rays.
Examples of the structure having infrared absorption or the compound having this structure include alkane, alkene (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumlen, cyclic), and alkyne (1). Substitution, bi-substituted), monocyclic aromatics (benzene, mono-substituted, di-substituted, tri-substituted), alcohols or phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds, saturated secondary, saturated tertiary). Class, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxylan ring ether, peroxide ether, ketone, dialkylcarbonyl, aromatic carbonyl, 1,3 -Diketone enol, o-hydroxyarylketone, dialkylaldehyde, aromatic aldehyde, carboxylic acid (dimer, carboxylic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β) -, Γ-, δ-), Aliphatic acid compounds, Aromatic acid compounds, Acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, Primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary Secondary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanic acid esters, thiocyanic acid esters, aliphatic isothiocyanate esters, aromatic isothiocyanate esters, aliphatic nitro compounds, Aromatic nitro compounds, nitroamines, nitrosamines, nitrates, nitrites, nitroso bonds (aliphatics, aromatics, monomers, dimers), sulfur compounds such as mercaptans or thiophenols or thiolic acids, thiocarbonyl groups, Sulfoxide, sulfone, sulfonyl chloride, primary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² Bonds (A ² is H, C or O) or Ti—O bonds can be mentioned.

Examples of the structure containing a carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF _2- , -CF ₃ , -CH = CF ₂ , -CF = CF ₂ , and fluorine. Aryl carbonate, aryl chloride and the like can be mentioned.

Examples of the structure including the above Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH _2- , Si—C 6H ₅ , SiO—aliphatic, Si _— OCH ₃ , Si-OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ or SiF ₃ and the like. As the structure containing the Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton or a silsesquioxane skeleton.

Examples of the structure containing the PA ² bond include PH, PH ₂ , P-CH ₃ , P-CH _2- , P-C ₆ H ₅ , A ³ ₃ -PO (A ³ is a fat). Group group or aromatic group), (A ⁴ O) ₃ -PO (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , P-O-P , P-OH or O = P-OH and the like.

Examples of the compound containing the Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate and the like. Alkoxytitanium; (iii) Di-i-propoxy-bis (acetylacetonato) titanium or chelated titanium such as propanedioxytitanium bis (ethylacetoacetate); (iii) i-C ₃ H ₇ O- [-Ti ( O-i-C ₃ H ₇ ) ₂ -O-] _n -i-C ₃ H ₇ or n-C ₄ H ₉ O- [-Ti (On-C ₄ H ₉ ) ₂ -O-] _n -Titanium polymers such as n-C 4H ₉ ; ( _iv ) tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate or (2-n-butoxycarbonylbenzoyloxy). Achilled titanium such as tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium and the like can be mentioned.
Among them, as a compound containing a Ti—O bond, di-n-butoxy-bis (triethanolamineto) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ ) is preferable.

The infrared-absorbing structure described above can absorb infrared rays having a wavelength in a desired range, depending on the type of the structure. Specifically, the wavelength of infrared rays that can be absorbed by the above-mentioned infrared-absorbing structure is, for example, in the range of 1 to 20 μm, and more preferably in the range of 2 to 15 μm.
Further, when the structure is Si—O bond, Si—C bond or Ti—O bond, it is preferably in the range of 9 to 11 μm.

Those skilled in the art can easily understand the wavelength of infrared rays that can be absorbed by each of the above structures. For example, as an absorption band in each structure, Non-Patent Documents: SILVERSTEIN, BASSLER, MORRRILL, "Identification Method by Spectrum of Organic Compounds (5th Edition) -Combination of MS, IR, NMR, UV-" (Published in 1992). References can be made to the description on pages 146 to 151.

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

-Infrared absorbing substance The separation layer may contain an infrared absorbing substance. The infrared absorber may be any substance that is altered by absorbing light, and for example, carbon black, iron particles, or aluminum particles can be preferably used.
The infrared absorber absorbs light having a wavelength in a unique range depending on the type. By irradiating the separation layer with light having a wavelength within the range absorbed by the infrared absorber used for the separation layer, the infrared absorber can be suitably altered.

-The reactive polysilsesquioxane separation layer can be formed by polymerizing the reactive polysilsesquioxane. The separation layer formed thereby has high chemical resistance and high heat resistance.

"Reactive polysilsesquioxane" refers to polysilsesquioxane having a silanol group at the end of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. .. By condensing the silanol group or the functional group capable of forming the silanol group, they can be polymerized with each other. Further, if the reactive polysilsesquioxane has a silanol group or a functional group capable of forming a silanol group, it can form a silsesquioxane skeleton having a random structure, a cage-shaped structure, a ladder structure or the like. The provided reactive polysilsesquioxane can be adopted.

The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol%, more preferably 80 to 99 mol%.
If the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably altered by irradiating with infrared rays (preferably far infrared rays, more preferably light having a wavelength of 9 to 11 μm). A possible separation layer can be formed.

The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, more preferably 1000 to 10000.
When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferable range, it can be suitably dissolved in a solvent and can be suitably applied on a support plate.

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

-Resin component having a phenol skeleton The separation layer may contain a resin component having a phenol skeleton. By having a phenol skeleton, it is easily altered (oxidized, etc.) by heating or the like, and the photoreactivity is enhanced.
As used herein, "having a phenol skeleton" means that it contains a hydroxybenzene structure.
The resin component having a phenol skeleton has a film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30000, still more preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is not more than the upper limit of the above-mentioned preferable range, the solubility of the composition for forming a separation layer in a solvent is enhanced.
As the molecular weight of the resin component, the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography) is used.

Examples of the resin component having a phenol skeleton include a novolak type phenol resin, a resole type phenol resin, a hydroxystyrene resin, a hydroxyphenylsilsesquioxane resin, a hydroxybenzylsilsesquioxane resin, a phenol skeleton-containing acrylic resin, and a general formula described later. Examples thereof include a resin having a repeating unit represented by (P2). Among these, novolak type phenol resin and resol type phenol resin are more preferable.

<Device layer>
The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Specifically, the device layer includes at least one of an encapsulant layer and a wiring layer, and may further include a substrate.
In the laminate 100 shown in FIG. 1, the device layer 456 is composed of a substrate 4, a sealing material layer 5, and a wiring layer 6. In the laminate 200 shown in FIG. 2, the device layer 45 is composed of the substrate 4 and the encapsulant layer 5. In the laminated body 300 shown in FIG. 3, the device layer is composed of the wiring layer 6. In the laminated body 400 shown in FIG. 4, the device layer 645 is composed of a wiring layer 6, a substrate 4, and a sealing material layer 5.

≪Board≫
The substrate (bare chip) is subjected to processes such as thinning and mounting while being supported by a support. Structures such as integrated circuits and metal bumps are mounted on the substrate.
As the substrate, a silicon wafer substrate is typically used, but the substrate is not limited to this, and a ceramic substrate, a thin film substrate, a flexible substrate, or the like may be used.

The substrate may be a semiconductor device or other device, and may have a single-layer or multi-layer structure. When the substrate is a semiconductor element, the electronic component obtained by dicing the device layer is a semiconductor device. Preferably, the substrate is a semiconductor device.

≪Encapsulant layer≫
The encapsulant layer is provided for encapsulating the substrate, and is formed by using the encapsulant. As the sealing material, a member capable of insulating or sealing a member made of metal or a semiconductor is used.
In the present embodiment, a resin composition containing a resin is used as the sealing material. The resin used for the encapsulant is not particularly limited as long as it can encapsulate and / or insulate a metal or semiconductor, and examples thereof include epoxy resins.
The encapsulant may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles and the like.

As shown in Examples described later, the resin used for the encapsulant has hygroscopicity and generates gas as the temperature rises (see FIG. 9A). It was also confirmed that most of the gas generated from the encapsulant was water vapor (see FIG. 9B). Therefore, the heat treatment step in the electronic component manufacturing process releases gas from the encapsulant, which causes voids. The laminate of the present embodiment is characterized in that an intermediate layer made of a material having a low water vapor permeability (that is, a material satisfying (Requirement 1-1)) is provided adjacent to the device layer, thereby sealing. It suppresses the release of gas from the stop material. Therefore, the generation of voids between the device layer and the support can be reduced.

≪Wiring layer≫
The wiring layer is also called an RDL (Redistribution Layer), and is a thin film wiring body constituting a wiring connected to a substrate, and may have a single layer or a plurality of layers. The wiring layer is formed between patterned resin materials (such as photosensitive polyimide and photosensitive acrylic resin) and conductors (eg, metals such as aluminum, copper, titanium, nickel, gold and silver, and silver-. The wiring may be formed of an alloy such as a tin alloy), but the wiring is not limited to this.

When the wiring layer is provided adjacent to the intermediate layer in the device layer, it is preferable that the dielectric in the wiring layer contains a resin. When the dielectric contains a hygroscopic resin such as an epoxy resin or a polyimide resin, gas is released from the resin by the heat treatment step, which causes voids. In the laminated body of the present embodiment, the emission of gas from the resin is suppressed by the intermediate layer adjacent to the device layer, so that the generation of voids can be reduced.

In the laminated body of FIGS. 1 to 3, the support substrate 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this, and another layer is further formed between the support substrate 1 and the separation layer 2. It may have been done. In this case, the other layer may be composed of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts preferable properties to the laminated body 100 without hindering the incident of light on the separation layer 2. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 2. Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from the materials transmitting light having a wavelength that can change the material constituting the separation layer 2.

(Laminated body (second aspect))
The laminate according to the second aspect of the present invention is a laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order, and at least the intermediate layer and the device layer are adjacent to each other. It is a thing. The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. The intermediate layer was prepared at 180 ° C. when a test piece having a thickness of 500 μm was prepared and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz. It is composed of a material that satisfies the requirement that the storage elastic modulus of 10000 (Pa · s) or more.

The laminate according to the second aspect has the same configuration as the laminate according to the first aspect, except that the intermediate layer is composed of an intermediate layer forming material satisfying the following (requirement 2-1).
(Requirement 2-1): When a test piece having a thickness of 500 μm was prepared and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz, 180. The melt viscosity at ° C. is 10,000 (Pa · s) or more.

The measurement of the melt viscosity in the above (Requirement 2-1) can be performed according to the same procedure as in "(Requirement 1-2)" in the laminate of the first aspect.

By providing an intermediate layer made of an intermediate layer forming material satisfying the above (Requirement 2-1) adjacent to the device layer, it is possible to effectively suppress the release of gas from the device layer. The melt viscosity in the above (requirement 1) is preferably 15,000 (Pa · s) or more, more preferably 20000 (Pa · s) or more, and even more preferably 25,000 (Pa · s) or more. The upper limit of the melt viscosity is not particularly limited, but is, for example, 50,000 (Pa · s) or less.

As the intermediate layer forming material, any known material can be used without particular limitation as long as it satisfies the above (Requirement 2-1) and can form a film. Examples of such a material include an elastomer resin and the like. Examples of such an elastomer resin include the same as those described in "<< Adhesive Composition >>" in the laminate of the first aspect.

The elastomer may be used in the intermediate layer as an elastomer composition by adding other components as appropriate. Examples of such other components include diluting solvents, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants and the like. As these, known ones can be used without particular limitation.

Examples of commercially available products of the elastomer resin composition that can be used as the material of the intermediate layer include "TZNR-A4007" manufactured by Tokyo Ohka Kogyo Co., Ltd.

The intermediate layer forming material preferably satisfies the following (requirement 2-2) in addition to the above (requirement 2-1).
(Requirement 2-2): At a temperature of 40 ° C. and a humidity of 90% RH, the water vapor permeability in terms of a thickness of 20 μm is 5 g / (m ² · day) or less.

The measurement of the water vapor transmittance in the above (requirement 2) can be performed according to the same procedure as in "(requirement 1)" in the laminate of the first aspect.

By satisfying (Requirement 2-2) in addition to the above (Requirement 2-1), outgassing from the device layer can be suppressed more effectively. The water vapor permeability in the above (requirement 2) is preferably 3 g / (m ² · day) or less, and more preferably 1 g / (m ² · day) or less. The lower limit of the water vapor transmittance is not particularly limited, but is, for example, 0.01 g / (m ² · day) or more.

The laminate of this embodiment is characterized in that an intermediate layer made of a material having a high melt viscosity (that is, a material satisfying (Requirement 2-1)) is provided adjacent to the device layer. Thereby, similarly to the laminated body of the first aspect, it is possible to suppress the release of gas from the device layer and reduce the generation of voids between the device layer and the support.

(Laminated body (third aspect))
The laminate according to the third aspect of the present invention is a laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order, and at least the intermediate layer and the device layer are adjacent to each other. It is a thing. The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. The intermediate layer contains a cycloolefin polymer.

The laminate according to the third aspect has the same configuration as the laminate according to the first aspect, except that the intermediate layer is composed of an intermediate layer forming material containing a cycloolefin polymer.

≪Cycloolefin polymer≫
Examples of the cycloolefin polymer include the same as those mentioned in "<Intermediate layer>" in the first aspect.
Preferred examples of the structural unit (u1) derived from the cycloolefin monomer contained in the cycloolefin polymer include the structural unit represented by the following general formula (u1-1).

［式中、Ｒ^ｕ１１～Ｒ^ｕ１４は、それぞれ独立に、炭素数１～３０の有機基又は水素原子を表す。ｎは、０～２の整数である。］

[In the formula, ^Ru11 to ^Ru14 each independently represent an organic group or a hydrogen atom having 1 to 30 carbon atoms. n is an integer of 0 to 2. ]

In the above formula (u1-1), the organic group in ^Ru11 to ^Ru14 has, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalinel group, a cycloalkyl group and a carboxy group. Examples thereof include an organic group and an organic group having a heterocycle.
The alkyl group in R ^u11 to ^Ru14 is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and the like. Examples thereof include a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like.
Examples of the alkenyl group in R ^u11 to R ^u14 include an allyl group, a pentaenyl group, a vinyl group and the like.
Examples of the alkynyl group in R ^u11 to R ^u14 include an ethynyl group and the like.
Examples of the alkylidene group in R ^u11 to R ^u14 include a methylidene group and an ethylidene group.
Examples of the aryl group in R ^u11 to R ^u14 include a phenyl group, a naphthyl group, an anthrasenyl group and the like.
Examples of the aralkyl group in R ^u11 to R ^u14 include a benzyl group and a phenethyl group.
Examples of the alkaline group in R ^u11 to R ^u14 include a tolyl group and a xylyl group.
Examples of the cycloalkyl group in R ^u11 to R ^u14 include an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
Examples of the organic group having a heterocycle in ^Ru11 to ^Ru14 include an organic group having an epoxy group, an organic group having an oxetanyl group and the like.

The organic group in ^Ru11 to ^Ru14 is preferably an alkyl group from the viewpoint of higher solubility in a hydrocarbon solvent and synthetic viewpoint. In addition, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 2 to 6 carbon atoms is further preferable because it is easy to maintain a high glass transition point.

In the organic groups in R ^u11 to R ^u14 , one or more hydrogen atoms may be substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As R ^u11 to R ^u14 , a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable.

In the above formula (u1-1), n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

A specific example of the structural unit (u1) is shown below.

Among the above, as the structural unit (u1), the structural unit represented by the formula (u1-1-1) is preferable. The structural unit (u1) contained in the cycloolefin polymer may be one kind or two or more kinds.

The ratio of the structural unit (u1) in the cycloolefin polymer is preferably 30 mol% or more, more preferably 40 mol% or more, based on all the structural units (100 mol%) constituting the cycloolefin polymer. When the content ratio of the structural unit (u1) is at least the lower limit of the above preferable range, outgassing from the device layer can be effectively suppressed. The upper limit of the content ratio of the structural unit (u1) is not particularly limited, but is, for example, 90 mol% or less with respect to all the structural units (100 mol%) constituting the cycloolefin polymer.
Further, the ratio of the constituent unit (u1) in the cycloolefin polymer may be 100 mol%.

In addition to the structural unit (u1), the cycloolefin polymer may have a structural unit derived from another monomer copolymerizable with the cycloolefin monomer.
Examples of such a structural unit include a structural unit (u2) derived from an alkene monomer. A preferable example of the structural unit (u2) is a structural unit represented by the following general formula (u2-1).

［式中、Ｒ^ｕ２１は、アルキル基又は水素原子を表す。］

[In the formula, ^Ru21 represents an alkyl group or a hydrogen atom. ]

In the general formula (u2-1), ^Ru21 is an alkyl group or a hydrogen atom.
The alkyl group in ^Ru21 may be linear or branched. The alkyl group in ^Ru21 is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or tert-butyl. Examples thereof include a group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like. Among these, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 or 2 carbon atoms is further preferable.
Preferred examples of R ^u21 include a methyl group, an ethyl group, or a hydrogen atom. Of these, a hydrogen atom is preferable for ^Ru21 .

The structural unit (u2) contained in the cycloolefin polymer may be one kind or two or more kinds.

The ratio of the structural unit (u2) in the cycloolefin polymer is preferably 70 mol% or less, more preferably 60 mol% or more, with respect to all the structural units (100 mol%) constituting the cycloolefin polymer. When the content ratio of the structural unit (u2) is at least the lower limit of the above preferable range, it becomes easy to balance with the structural unit (u1). The lower limit of the content ratio of the structural unit (u2) is not particularly limited, but is, for example, 10 mol% or more with respect to all the structural units (100 mol%) constituting the cycloolefin polymer.

In the present embodiment, the cycloolefin polymer is preferably a copolymer of a cycloolefin monomer and an alkene monomer, and the copolymer comprises the structural units (u1) and (u2).

Specific examples of the cycloolefin polymer are shown below.

In the present embodiment, the intermediate layer forming material containing the cycloolefin polymer is preferably a cycloolefin polymer composition satisfying the following (requirement 3-1).
(Requirement 3-1): At a temperature of 40 ° C. and a humidity of 90% RH, the water vapor permeability in terms of a thickness of 20 μm is 5 g / (m ² · day) or less.

The measurement of the water vapor transmittance in the above (requirement 3-1) can be performed according to the same procedure as in "(requirement 1-1)" in the laminate of the first aspect.

By using a cycloolefin polymer composition satisfying the above (requirement 3-1), outgassing from the device layer can be suppressed more effectively. The water vapor permeability in the above (requirement 3-1) is preferably 3 g / (m ² · day) or less, and more preferably 1 g / (m ² · day) or less. The lower limit of the water vapor transmittance is not particularly limited, but is, for example, 0.01 g / (m ² · day) or more.

Further, the cycloolefin polymer composition preferably satisfies the following requirement (3-2) in addition to the above requirement (3-1).
(Requirement 3-2): When a test piece having a thickness of 500 μm was prepared and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz, 180. The melt viscosity at ° C. is 10,000 (Pa · s) or more.

The measurement of the melt viscosity in the above (Requirement 3-2) can be performed according to the same procedure as in "(Requirement 1-2)" in the laminate of the first aspect.

By using a cycloolefin polymer composition satisfying (Requirement 3-2) in addition to the above (Requirement 3-1), outgassing from the device layer can be suppressed more effectively. The melt viscosity in the above (Requirement 3-2) is preferably 15,000 (Pa · s) or more, more preferably 20000 (Pa · s) or more, and even more preferably 25,000 (Pa · s) or more. The upper limit of the melt viscosity is not particularly limited, but is, for example, 50,000 (Pa · s) or less.

Further, the cycloolefin polymer preferably has a glass transition temperature (Tg) of 90 ° C. or higher.
The glass transition temperature (Tg / ° C.) for the resin component is determined by dynamic viscoelasticity measurement. For example, using a dynamic viscoelasticity measuring device Rheologel-E4000 (manufactured by UBM Co., Ltd.), measurement is performed by raising the temperature from 25 ° C to 300 ° C at a temperature rising rate of 5 ° C / min under the condition of a frequency of 1 Hz. It can be obtained based on the change in viscoelasticity.

When the glass transition temperature (Tg) of the cycloolefin polymer is 90 ° C. or higher, outgassing from the device layer can be suppressed more effectively. The glass transition temperature (Tg) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 130 ° C. or higher. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is, for example, 250 ° C. or lower.

The intermediate layer forming material may contain other components in addition to the cycloolefin polymer. Examples of such other components include diluting solvents, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants and the like. As these, known ones can be used without particular limitation. Examples of the diluting solvent include those mentioned in "<< Adhesive layer >>" in the laminate of the first aspect.

The laminate of this embodiment is characterized in that an intermediate layer made of a material containing a cycloolefin polymer is provided adjacent to the device layer. Thereby, similarly to the laminated body of the first and second aspects, it is possible to suppress the release of gas from the device layer and reduce the generation of voids between the device layer and the support.

(Manufacturing method of laminated body)
The method for manufacturing a laminated body according to the fourth to sixth aspects of the present invention is a method for manufacturing a laminated body in which a support, an adhesive layer, an intermediate layer and a device layer are laminated in this order, and is a bonding layer forming step and a device layer forming. Includes steps, intermediate layer forming steps and device layer fixing steps. The method for manufacturing the laminate may further include a grinding step, a wiring layer forming step, a separating layer forming step, and the like.

The method for producing the laminate according to the fourth aspect is the method for producing the laminate according to the first aspect, and the thickness is converted to 20 μm at a temperature of 40 ° C. and a humidity of 90% RH as an intermediate layer forming material. Use a material that meets the requirement that the value of water vapor permeability is 5 g / (m ² · day) or less.
The method for producing the laminate according to the fifth aspect is the method for producing the laminate according to the second aspect, wherein a test piece having a thickness of 500 μm is produced as an intermediate layer forming material, and the starting temperature is 25 ° C. A material that meets the requirements of a melt viscosity of 10,000 (Pa · s) or more at 180 ° C. when subjected to dynamic viscoelasticity measurement under the conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz is used.
The method for producing the laminate according to the sixth aspect is the method for producing the laminate according to the third aspect, and a material containing a cycloolefin polymer is used as the intermediate layer forming material.
The method for producing the laminate according to the fourth to sixth aspects can be performed by the same step except that the intermediate layer forming material used in the intermediate layer forming step is as described above.

5 to 7 are schematic process diagrams illustrating an embodiment of the method for manufacturing a laminated body according to the present embodiment.
FIG. 5 is a diagram illustrating a manufacturing process of a support 123 with an adhesive layer composed of a support 12 and an adhesive layer 3. FIG. 5A is a diagram illustrating a separation layer forming step, and FIG. 5B is a diagram illustrating an adhesive layer forming step.
FIG. 6 is a diagram illustrating a process of manufacturing the laminated body 100 from the support 123 with an adhesive layer. FIG. 6A is a diagram showing a support 123 with an adhesive layer, FIG. 6B is a diagram illustrating an intermediate layer forming step, and FIG. 6C is a diagram illustrating a device layer fixing step. It is a figure to do.
FIG. 7 is a diagram illustrating a process of manufacturing the laminated body 200 from the laminated body 100. 7 (a) is a diagram showing the laminated body 100, FIG. 7 (b) is a diagram for explaining a grinding process, and FIG. 7 (c) is a diagram for explaining a wiring layer forming process.

[Separation layer forming step]
The method for producing a laminate according to the present embodiment may include a separation layer forming step. The separation layer forming step is a step of forming a separation layer on one side of the support substrate using the composition for forming the separation layer.
In FIG. 5A, the separation layer 2 is formed on the support substrate 1 by using the composition for forming the separation layer. As a result, the support 12 composed of the support substrate 1 and the separation layer 2 is manufactured.

The method for forming the separation layer 2 on the support substrate 1 is not particularly limited, and examples thereof include spin coating, dipping, roller blades, spray coating, slit coating, and chemical vapor deposition (CVD).
For example, in the separation layer forming step, the solvent component is removed from the coating layer of the separation layer forming composition coated on the support substrate 1 under a heating environment or a reduced pressure environment to form a film, or the support substrate 1 is formed. The support 12 can be obtained by forming a film on the film by a vapor deposition method.

If the separation layer is unnecessary due to the use of an adhesive layer or an intermediate layer having the function of a separation layer, the separation layer forming step can be omitted. In this case, the support substrate 1 may be used as a support.

[Adhesive layer forming process]
The method for producing a laminated body according to the present embodiment includes an adhesive layer forming step. The adhesive layer forming step is a step of forming an adhesive layer on the support using the adhesive composition. If the support has a separation layer, the adhesive layer is formed on the surface of the support that has the separation layer.
In FIG. 5B, the adhesive layer 3 is formed on the surface of the support 12 on the separation layer 2 side by using the adhesive composition. As a result, the support 123 with an adhesive layer is produced.

The method for forming the adhesive layer 3 on the support 12 is not particularly limited, and examples thereof include spin coating, dipping, roller blades, spray coating, and slit coating. Then, the adhesive composition is applied onto the support 12 and heated, or the solvent component contained in the adhesive composition is removed under a reduced pressure environment.

After that, when the adhesive layer contains a curable monomer and a thermal polymerization initiator, the curable monomer may be polymerized by heating. The conditions for heating the adhesive layer 3 may be appropriately set based on the 1-minute half temperature and the 1-hour half temperature of the thermal polymerization initiator. The heating is preferably performed under vacuum or in an atmosphere of an inert gas such as nitrogen gas, more preferably in an atmosphere of an inert gas, at a temperature in the range of, for example, 50 to 300 ° C.

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

[Device layer forming process]
The method for manufacturing a laminate according to the present embodiment includes a device layer forming step. The device layer forming step is a step of forming a device layer, which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.
The device layer forming step can include a sealing step of sealing the substrate with a sealing material. For example, in FIG. 6B, the device layer 45 (sealing body) is formed by sealing the substrate 4 with a sealing material.

<Sealing process>
The sealing step is a step of producing a sealed body by sealing the substrate with a sealing material. The sealed body is used as the device layer 45 in the method for manufacturing a laminated body according to the present embodiment. The number of substrates to be sealed with the encapsulant is not particularly limited, and may be any number required to form the desired device layer.

In the sealing step, for example, the substrate is placed on the holding plate, and the sealing material heated to 130 to 170 ° C. is placed on the holding plate so as to cover the substrate 4 while maintaining a high viscosity state. A sealed body is produced by being supplied to and compression-molded.
At that time, the temperature condition is, for example, 130 to 170 ° C.
The pressure applied to the substrate 4 is, for example, 50 to 500 N / cm ² .

The device layer forming step may include a grinding step, a wiring layer forming step, and the like, which will be described later.

[Intermediate layer forming process]
The method for producing a laminate according to the present embodiment includes an intermediate layer forming step. The intermediate layer forming step is a step of forming an intermediate layer on the device layer or the adhesive layer by using the intermediate layer forming material.
In FIG. 6B, the intermediate layer 10 is formed on the device layer 45 (sealed body) by using the intermediate layer forming material. As a result, the laminated body 20 composed of the device layer 45 and the intermediate layer is produced. The intermediate layer 10 may be formed on the adhesive layer 3 of the support 123 with an adhesive layer. From the viewpoint of adhesiveness in the device layer fixing step described later, the intermediate layer 10 is preferably formed on the device layer 45.

In the intermediate layer forming step, any of the intermediate layer forming materials described in the above-mentioned laminates of the first to third aspects is used as the intermediate layer forming material, and the intermediate layer 10 is placed on the device layer 45 or the adhesive layer 3. To form.
The method for forming the intermediate layer 10 on the device layer 45 or the adhesive layer 3 is not particularly limited, and for example, a method such as spin coating, dipping, roller blade, spray coating, slit coating, chemical vapor deposition (CVD), or the like. Can be mentioned. When an inorganic substance is used as the intermediate layer forming material, examples of the method for forming the intermediate layer 10 include sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating and the like.
For example, in the intermediate layer forming step, the solvent component is removed from the coating layer of the intermediate layer forming material coated on the device layer 45 or the adhesive layer 3 under a heating environment or a reduced pressure environment to form a film. The intermediate layer 10 can be formed on the device layer 45 or the adhesive layer 3 by forming a film on the device layer 45 or the adhesive layer 3 by a vapor deposition method.

According to the method for manufacturing a laminate according to the present embodiment, since the intermediate layer is formed by using the above-mentioned intermediate layer forming material, the encapsulant layer is formed even when high temperature treatment is performed in the subsequent steps. It is possible to suppress the release of gas from. Therefore, it is possible to prevent voids from being generated between the support and the device layer, and the subsequent process can be preferably performed.

[Device layer fixing process]
The method for manufacturing a laminated body according to the present embodiment includes a device layer fixing step. The device layer fixing step is a step of fixing the device layer 45 (sealed body) on the support 12 via the adhesive layer 3 and the intermediate layer 10. Thereby, the laminated body 100 can be obtained.
In FIG. 6C, the support 123 with an adhesive layer and the laminated body 20 are bonded to each other, and the device layer 45 is fixed on the support 12 via the adhesive layer 3 and the intermediate layer 10 to be laminated. I'm getting 100 bodies.

The method of fixing the device layer 45 on the support 12 via the adhesive layer 3 and the intermediate layer 10 is not particularly limited, and a known method used for adhering the substrate or the like may be used. For example, the adhesive layer 3 and the intermediate layer 10 face each other, the device layer 45 is arranged at a predetermined position on the support 12, and the support 12 is heated by a die bonder or the like while being heated under vacuum (for example, about 100 ° C.). This can be done by crimping with the substrate 4.

[Arbitrary process]
The method for producing a laminate according to the present embodiment may include other steps in addition to the above steps. Examples of other steps include a grinding step, a wiring layer forming step, and the like. The grinding step and the wiring layer forming step may be performed in the device layer forming step.

<Grinding process>
The grinding step is a step of grinding the sealing material portion (sealing material layer 5) in the device layer so that a part of the substrate is exposed after the device layer fixing step.
Grinding of the encapsulant portion is performed, for example, by grinding the encapsulant layer 5 to a thickness substantially equal to that of the substrate 4, as shown in FIG. 7 (b).

<Wiring layer forming process>
The wiring layer forming step is a step of forming a wiring layer on the device layer after the device layer fixing step. In the wiring layer forming step, it is preferable to form the wiring layer on the exposed substrate after the grinding step.
In FIG. 7C, the wiring layer 6 is formed on the substrate 4 and the encapsulant layer 5. Thereby, the laminated body 200 can be obtained. In the laminated body 200, the substrate 4, the sealing material layer 5, and the wiring layer 6 constitute the device layer 456.

Examples of the method for forming the wiring layer 6 include the following methods.
First, a dielectric layer such as silicon oxide (SiO _x ) or a photosensitive resin is formed on the encapsulant layer 5. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by applying the photosensitive resin on the sealing material layer 5 by, for example, spin coating, dipping, roller blades, spray coating, slit coating, or the like. ..

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

In this way, when performing photolithography treatment, etching treatment, etc., the laminate is used as an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist solvent for dissolving the resist material. As it is exposed, it is treated at high temperatures.
However, by forming the intermediate layer 10 using the above-mentioned intermediate layer forming material, the movement of the gas released from the encapsulant is suppressed. Therefore, it is possible to prevent the generation of voids between the device layer 45 and the support 12, and the wiring layer 6 can be suitably formed.

According to the method for manufacturing a laminated body according to the present embodiment, the support 12, the adhesive layer 3, the intermediate layer 10, the device layer 45 (the substrate 4 and the encapsulant layer 5) or the device layer 456 (the substrate 4, the substrate 4,) A laminated body in which the sealing material layer 5 and the wiring layer 6) are laminated in this order can be stably manufactured.
Such a laminated body is a laminated body manufactured in a process based on a fan-out type technology in which terminals provided on the substrate 4 are mounted on a wiring layer 6 extending outside the chip area.

In the method for manufacturing a laminated body according to the present embodiment, bumps can be further formed or elements can be mounted on the wiring layer 6. The element can be mounted on the wiring layer 6 by using, for example, a chip mounter or the like.

Further, in the above-mentioned method for manufacturing a laminated body, a wiring layer forming step is performed after the device layer fixing step and the grinding step, but after the adhesive layer forming step, a wiring layer forming step is performed in the device layer forming step. After that, the intermediate layer forming step and the device layer fixing step may be performed to obtain the laminated body 300 shown in FIG. In this case, the wiring layer forming step may be followed by a sealing step and a grinding step to obtain the laminated body 400 shown in FIG. In the sealing step in this embodiment, the substrate is placed on the wiring layer and sealed with a sealing material.

(Manufacturing method of electronic parts)
The method for manufacturing an electronic component according to a seventh aspect is as follows: after obtaining the laminate according to any one of the first to third aspects by the method for manufacturing a laminate according to any one of the fourth to sixth aspects. It has a separation step and a removal step.

FIG. 8 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). 8 (a) and 8 (b) are diagrams for explaining the separation step, and FIG. 8 (c) is a diagram for explaining the removal step.

[Separation process]
The separation step is a step of irradiating the separation layer 2 with light (arrows) via the support substrate 1 to change the quality of the separation layer 2 to separate the device layer 456 and the support substrate 1.
In FIG. 8A, the separation layer 2 is altered by irradiating the separation layer 2 with light (arrows) via the support substrate 1.

Examples of the wavelength at which the separation layer 2 can be altered include a range of 600 nm or less.
The type and wavelength of the light to be irradiated may be appropriately selected depending on the transparency of the support substrate 1 and the material of the separation layer 2. For example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and a fiber. It is possible to use solid lasers such as lasers, liquid lasers such as dye lasers, gas lasers such as CO ₂ lasers, excima lasers, Ar lasers and He-Ne lasers, laser light such as semiconductor lasers and free electron lasers, and non-laser light. can. As a result, the separation layer 2 can be altered so that the support substrate 1 and the device layer 456 can be easily separated.

When irradiating a laser beam, the following conditions can be mentioned as an example of the laser beam irradiation conditions.
The average output value of the laser beam is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser beam is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less.

After irradiating the separation layer 2 with light (arrow) to change the quality of the separation layer 2, the support substrate 1 is separated from the device layer 456 as shown in FIG. 8 (b).
For example, the support substrate 1 and the device layer 456 are separated from each other by applying a force in a direction in which the support substrate 1 and the device layer 456 are separated from each other. Specifically, the support substrate 1 and the device are lifted while one of the support substrate 1 or the device layer 456 side is fixed to the stage and the other is suction-held by a separation plate equipped with a suction pad such as a bellows pad. It can be separated from the layer 456.
The force applied to the laminated body 100 may be appropriately adjusted depending on the size of the laminated body 100 and the like, and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, 0.1 to 5 kgf (0). By applying a force of about .98 to 49N), the support substrate 1 and the device layer 456 can be suitably separated.

[Removal process]
The removal step is a step of removing the separation layer, the adhesive layer, and the intermediate layer adhering to the device layer after the separation step.
FIG. 6B shows a state in which the separation layer 2, the adhesive layer 3 and the intermediate layer 10 are attached and remain on the device layer 456 after the separation step. In FIG. 8C, the electronic component 50 is obtained by removing the separation layer 2, the adhesive layer 3, and the intermediate layer 10 adhering to the device layer 456 in the removal step.

Examples of the method for removing the adhesive layer 3 and the like adhering to the device layer 456 include a method of removing the residue of the separation layer 2, the adhesive layer 3 and the intermediate layer 10 using a cleaning liquid.
As the cleaning liquid, a cleaning liquid containing an organic solvent is preferably used. As the organic solvent in this cleaning liquid, it is preferable to use a solvent component blended in the composition for forming a separation layer, a solvent component blended in the composition for forming an adhesive layer, a solvent component blended in the intermediate layer forming material, and the like.

In the method for manufacturing an electronic component of the present embodiment, after the above removing step, the electronic component 50 may be further subjected to treatments such as solder ball formation, dicing, and oxide film formation.

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

(Evaluation of outgassing of mold material)
The mold material containing the epoxy resin was cut into 1 cm x 1 cm squares, and the water content was measured using TDS1200 manufactured by ESCO. The temperature was changed from 40 ° C. to 300 ° C. at a heating rate of 0.5 ° C./sec.

The results are shown in FIG. FIG. 9A shows the total amount of gas released from the mold material, and FIG. 9B shows the amount of water vapor released from the encapsulant. As shown in FIGS. 9 (a) and 9 (b), it was confirmed that the total amount of gas released from the molding material and the amount of water vapor released increased with the temperature rising, peaking at around 150 to 180 ° C. .. The total gas release amount and the water vapor release amount decreased by the dehydration treatment by baking, but the release amount increased one day after the dehydration treatment. Further, from FIGS. 9 (a) and 9 (b), it was confirmed that most of the gas released from the encapsulant was water vapor.

(Example 1, Comparative Examples 1 and 2)
<Manufacturing of laminated body>
[Adhesive layer forming process]
The adhesive layer shown in Example 1 of Table 2 was produced on a glass-supported substrate (size diameter 30 cm, thickness 700 μm) while rotating at 1000 rpm by a spin coating method.
Then, the support substrate coated with the adhesive composition of each example was heated at 90 ° C. for 4 minutes, 160 ° C. for 4 minutes, and 220 ° C. for 4 minutes, respectively, to obtain the thickness of each example shown in Table 2. An adhesive layer was formed.

[Intermediate layer forming process]
The intermediate layer shown in Example 1 of Table 2 was applied onto a molded substrate sealed with an epoxy encapsulant while rotating at 1000 rpm by a spin coating method.
Next, the support substrate coated with the intermediate layer forming material was heated at 90 ° C. for 4 minutes, 160 ° C. for 4 minutes, and 220 ° C. for 4 minutes, respectively, to obtain an intermediate layer having a thickness shown in Example 1 of Table 2. Formed.

[Formation of laminated body]
The glass support substrate and the molded substrate formed as described above were laminated while the adhesive layer and the intermediate layer faced each other, and then heated to 215 ° C. using a sticking device under a reduced pressure condition of a pressure lower than 10 Pa. It was pressed with a pressing plate (300 mmφ) and compressed for 3 minutes while applying a force of 4 tons to obtain a laminate of each example shown in Table 2 (Example 1).
In Comparative Example 1, the glass support substrate and the molded substrate were laminated via only A4007, but this example could not be attached.
Further, in Comparative Example 2, the glass support substrate and the molded substrate are laminated via an adhesive layer made of A4017 having a thickness of 50 μm.

<Evaluation>
The laminated body of each example was heat-treated, and it was evaluated whether voids were generated between the support substrate and the sealing substrate. In addition, the melt viscosity, water vapor transmittance, and glass transition temperature (Tg) of the adhesive composition / intermediate layer forming material used for the laminate of each example were measured. These results are shown in Tables 2 and 3, respectively.

[Void generation test]
The laminates of each example were heat-treated for 1 hour under temperature conditions of 150 ° C., 180 ° C., or 200 ° C. After the heat treatment, the generation of voids in the adhesive layer was visually evaluated according to the evaluation criteria shown below. The evaluation results are shown in Table 2.
Evaluation criteria ○: No void ×: Void generation

[Measurement of melt viscosity]
For the adhesive composition / intermediate layer forming material of each example, the melt viscosities at 150 ° C., 180 ° C., and 200 ° C. were measured using a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM Co., Ltd.). ..
First, the adhesive composition / intermediate layer forming material was applied onto a PET film with a mold release agent, and heated in an oven under atmospheric pressure at 50 ° C. and 150 ° C. for 60 minutes each to form a test piece layer. (Thickness 500 μm). Then, the melt viscosity of the test piece peeled off from the PET film was measured using the above-mentioned dynamic viscoelasticity measuring device.
The measurement conditions were a tension condition with a frequency of 1 Hz, and a condition in which the temperature was raised from a starting temperature of 50 ° C. to 300 ° C. at a speed of 5 ° C./min.

[Water vapor permeability]
Based on the above-mentioned method (JIS K7129B), the water vapor permeability of the adhesive composition / intermediate layer forming material of each example was obtained in terms of thickness 20 μm and thickness 50 μm, respectively, and is shown in Table 3. The water vapor transmittance is shown as a value under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.

[Measurement of glass transition temperature (Tg)]
For the adhesive composition / intermediate layer forming material of each example, a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) was used, and the temperature was 25 ° C./min at a temperature of 5 ° C./min. The glass transition temperature was determined based on the change in viscoelasticity measured by increasing the temperature from ° C to 300 ° C. The results are shown in Table 3.

In Tables 2 and 3, each abbreviation has the following meaning.
A4007: TZNR-A4007 (trade name), manufactured by Tokyo Ohka Kogyo Co., Ltd .; elastomer adhesive.
A4017: TZNR-A4017 (trade name), manufactured by Tokyo Ohka Kogyo Co., Ltd .; elastomer adhesive.

From the results shown in Tables 2 and 3, it was confirmed that the laminate of Example 1 can suppress the generation of gas from the sealed substrate and prevent the generation of voids at any temperature.
On the other hand, in Comparative Example 1, the sealed substrate could not be attached to the support substrate, and the laminate could not be produced. In Comparative Example 2, voids were generated at any temperature.

(Examples 2 to 3, reference examples 1 to 3)
<Preparation of resin composition>
The resin components shown in Table 4 were dissolved in a solvent (decahydronaphthalene) at a solid content concentration of 30% to prepare resin compositions of each example. Further, a film was formed from the resin composition of each example, and the water vapor transmittances of the thickness 5 μm conversion value, the thickness 20 μm conversion value, and the thickness 50 μm conversion value were measured by the same method as described above. The results are shown in Table 4.

In Table 4, each abbreviation has the following meaning. The glass transition temperature (° C.) for the resin components shown below was determined in the same manner as above.

(P) -1: APL8008T (trade name) manufactured by Mitsui Chemicals, Inc. Glass transition temperature 75 ° C., weight average molecular weight 80000; cycloolefin polymer represented by the following chemical formula (P) -1 (m: n = 80: 20 (molar ratio)).

(P) -2: APL6013T (trade name) manufactured by Mitsui Chemicals, Inc. Glass transition temperature 125 ° C., weight average molecular weight 60000; cycloolefin polymer represented by the following chemical formula (P) -2 (m: n = 65: 35 (molar ratio)).

(P) -3: APL6015T (trade name) manufactured by Mitsui Chemicals, Inc. Glass transition temperature 145 ° C., weight average molecular weight 60000; cycloolefin polymer represented by the following chemical formula (P) -3 (m: n = 58: 42 (molar ratio)).

<Manufacturing of laminated body>
The laminates of each example shown in Table 5 were produced by the same method as above except that the compositions of each example shown in Tables 5 and 6 were used as the adhesive composition and the intermediate layer forming material.

<Evaluation>
The laminated body of each example was heat-treated, and a void generation test was conducted by the same method as described above. The results are shown in Tables 5 and 6. In Table 5, "A4017" is the same as that in Table 2. The evaluation criteria are as follows.
Evaluation criteria ○: No void ×: Void generation

From the results shown in Table 5, it was confirmed that the laminate of Example 3 can suppress the generation of gas from the sealed substrate and prevent the generation of voids at any temperature. It was confirmed that even the laminate of Example 2 can prevent the generation of voids up to a temperature of up to 150 ° C.
On the other hand, in Reference Examples 1 and 2, voids were generated at 150 ° C. or higher. In Reference Example 3, the sealing substrate could not be attached to the support substrate, and the laminate could not be produced.

1 Support substrate,
2 Separation layer,
3 Adhesive layer,
4 board,
5 Encapsulant layer,
6 wiring layer,
10 middle layer,
12 Support,
20 laminated body,
45 device layer 50 electronic components,
100 laminates,
200 laminates,
300 laminated body,
400 laminate,
123 Support with adhesive layer 456 Device layer 645 Device layer.

Claims (15)

A laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order.
At least, the intermediate layer and the device layer are adjacent to each other,
The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.
The intermediate layer is a laminate made of a material that satisfies the requirement that the water vapor transmittance in terms of thickness 20 μm is 5 g / (m ² · day) or less at a temperature of 40 ° C. and a humidity of 90% RH. A laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order.
At least, the intermediate layer and the device layer are adjacent to each other,
The device layer is a composite of a member made of metal or a semiconductor and a resin that seals or insulates the member. The intermediate layer prepares a test piece having a thickness of 500 μm, and starts at a starting temperature of 25 ° C. It is made of a material that meets the requirements that the melt viscosity at 180 ° C is 10,000 (Pa · s) or more when subjected to dynamic viscoelasticity measurement under the conditions of temperature rise rate: 5 ° C / min and frequency: 1 Hz. Laminated body. A laminate in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order.
At least, the intermediate layer and the device layer are adjacent to each other,
The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member, and the intermediate layer contains a cycloolefin polymer.
As the intermediate layer forming material containing the cycloolefin polymer constituting the intermediate layer, a test piece having a thickness of 500 μm was prepared, and the starting temperature was 25 ° C., the heating rate was 5 ° C./min, and the frequency was 1 Hz. A laminate that satisfies the requirement that the melt viscosity at 180 ° C. be 10,000 (Pa · s) or more when subjected to viscoelasticity measurement . The laminate according to claim 3, wherein the cycloolefin polymer is a copolymer of a cycloolefin monomer and an alkene monomer. The fourth aspect of the present invention, wherein the proportion of the constituent units derived from the cycloolefin monomer in the copolymer is 30 mol% or more with respect to all the constituent units (100 mol%) constituting the copolymer. Laminated body. The adhesive layer was prepared at 180 ° C. when a test piece having a thickness of 500 μm was prepared and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz. The laminate according to any one of claims 1 to 5, which is made of a material having a melt viscosity of 1000 (Pa · s) or more and 10000 (Pa · s) or less. The ratio of the thickness (μm) of the adhesive layer to the thickness (μm) of the intermediate layer is any one of claims 1 to 6, wherein the adhesive layer / intermediate layer = 1/9 to 9/1. The laminate described in. The support has a support substrate that transmits light and a separation layer that is formed on the support substrate and is altered by irradiation with light, and the separation layer and the adhesive layer are provided so as to be adjacent to each other. The laminate according to any one of claims 1 to 7. A method for manufacturing a laminated body in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order.
An adhesive layer forming step of forming an adhesive layer on a support using an adhesive composition,
A device layer forming step of forming a device layer, which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.
An intermediate layer forming step of forming an intermediate layer on the device layer or the adhesive layer by using the intermediate layer forming material.
A device layer fixing step of fixing the device layer on the support via the adhesive layer and the intermediate layer is included.
The intermediate layer forming material is a material that satisfies the requirement that the water vapor transmittance in terms of thickness 20 μm is 5 g / (m ² · day) or less at a temperature of 40 ° C. and a humidity of 90% RH.
A method for manufacturing a laminate. A method for manufacturing a laminated body in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order.
An adhesive layer forming step of forming an adhesive layer on a support using an adhesive composition,
A device layer forming step of forming a device layer, which is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member.
An intermediate layer forming step of forming an intermediate layer on the device layer or the adhesive layer by using the intermediate layer forming material.
A device layer fixing step of fixing the device layer on the support via the adhesive layer and the intermediate layer is included.
When the intermediate layer forming material produced a test piece having a thickness of 500 μm and subjected to dynamic viscoelasticity measurement under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz, 180. A material that meets the requirement that the melt viscosity at ° C be 10,000 (Pa · s) or more.
A method for manufacturing a laminate. A method for manufacturing a laminated body in which a support, an adhesive layer, an intermediate layer, and a device layer are laminated in this order.
A device that is a composite of an adhesive layer forming step of forming an adhesive layer on a support using an adhesive composition, a member composed of a metal or a semiconductor, and a resin that seals or insulates the member. Device layer forming process to form a layer,
An intermediate layer forming step of forming an intermediate layer on the device layer or the adhesive layer by using the intermediate layer forming material.
A device layer fixing step of fixing the device layer on the support via the adhesive layer and the intermediate layer is included.
The intermediate layer forming material is a material containing a cycloolefin polymer, and a test piece having a thickness of 500 μm is prepared and dynamically operated under the conditions of a starting temperature of 25 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz. Satisfies the requirement that the melt viscosity at 180 ° C. be 10,000 (Pa · s) or more when subjected to viscoelasticity measurement.
A method for manufacturing a laminate. The device layer is a complex of a substrate made of a semiconductor and a resin that seals the substrate.
After the device layer fixing step, further
The device includes a wiring layer forming step of forming a wiring layer which is a composite of a wiring composed of metal and a resin for insulating the wiring on the device layer.
The method for producing a laminate according to any one of claims 9 to 11. After the device layer fixing step and before the wiring layer forming step, a grinding step of grinding a resin portion sealing the substrate so that a part of the substrate is further exposed is included.
The method for manufacturing a laminate according to claim 12. The support is composed of a support substrate and a separation layer that is altered by irradiation with light.
The method for producing a laminated body according to any one of claims 9 to 13, wherein the adhesive layer forming step is a step of forming an adhesive layer on the separation layer. After obtaining the laminated body by the manufacturing method according to claim 14,
A separation step of separating the support substrate from the device layer included in the laminate by irradiating the separation layer with light through the support substrate to change the quality of the separation layer.
After the separation step, a removal step of removing the adhesive layer and the intermediate layer adhering to the device layer, and
Manufacturing methods for electronic components, including.

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