WO2020070790A1 - Produit stratifié et procédé de production d'un corps d'étanchéité durci - Google Patents

Produit stratifié et procédé de production d'un corps d'étanchéité durci

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Publication number
WO2020070790A1
WO2020070790A1 PCT/JP2018/036812 JP2018036812W WO2020070790A1 WO 2020070790 A1 WO2020070790 A1 WO 2020070790A1 JP 2018036812 W JP2018036812 W JP 2018036812W WO 2020070790 A1 WO2020070790 A1 WO 2020070790A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
resin layer
energy ray
cured
curable resin
Prior art date
Application number
PCT/JP2018/036812
Other languages
English (en)
Japanese (ja)
Inventor
明徳 佐藤
洋佑 高麗
高志 阿久津
康彦 垣内
岡本　直也
忠知 山田
中山　武人
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201880098044.9A priority Critical patent/CN112789334B/zh
Priority to KR1020217007633A priority patent/KR102543787B1/ko
Priority to PCT/JP2018/036812 priority patent/WO2020070790A1/fr
Priority to JP2020550976A priority patent/JP7129110B2/ja
Publication of WO2020070790A1 publication Critical patent/WO2020070790A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to a method for producing a laminate and a cured sealing body.
  • CSP Chip Scale Package
  • WLP Wafer Level Package
  • PLP Panel Level Package
  • WLP and PLP are classified into a fan-in type and a fan-out type.
  • a fan-out type WLP hereinafter, also referred to as “FOWLP”
  • a PLP hereinafter, also referred to as “FOLP”
  • a sealing material so as to have an area larger than the chip size.
  • a rewiring layer and external electrodes are formed not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material.
  • FOWLP and FOPLP are, for example, a placing step of placing a plurality of semiconductor chips on a temporary fixing sheet, a covering step of covering with a thermosetting sealing material, and a thermosetting curing of the sealing material.
  • Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting electronic components, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a substrate.
  • a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a substrate.
  • use of the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 is also conceivable.
  • the cured sealing body tends to warp due to heat shrinkage. This is because the semiconductor chip sealed in the cured sealing body is unevenly located on the surface side in contact with the temporary fixing sheet. A region where the ratio is relatively high and a region where the presence ratio of the cured resin having a large thermal expansion coefficient is relatively high occur, and a stress is generated due to a difference in the thermal shrinkage ratio between the two regions. Conceivable. This problem tends to become more pronounced as the package size increases, such as FOWLP and FOPLP.
  • the warped cured sealing body is, for example, easily cracked when the cured sealing body is ground in the next step, and is cured by the arm when the cured sealing body is transported by the device. A harmful effect may occur, such as an inconvenience during the delivery of the body.
  • a method of suppressing the warpage of the cured sealing body for example, a method of using a laminate including a temporary fixing layer provided with a thermally expandable pressure-sensitive adhesive layer containing thermally expandable particles and a thermosetting resin layer is also considered.
  • a mounting step and a covering step of the semiconductor chip are performed on the thermosetting resin layer provided in the laminate, and thereafter, the thermosetting resin layer and the sealing material are heat-cured to form a cured seal with the cured resin layer.
  • the thermally expandable particles are expanded to separate the cured sealing body with the cured resin layer from the temporary fixing layer.
  • the cured resin layer functions as a warp preventing layer of the cured sealing body, a cured sealing body in which the occurrence of warpage is suppressed can be obtained.
  • the treatment for expanding the thermally expandable particles and the treatment for curing the thermosetting resin layer are both heat treatments, so that the thermosetting resin layer is cured.
  • the heat-expandable particles in the temporary fixing layer are foamed during the heat treatment.
  • the thermally expandable particles in the temporary fixing layer expand, the separability of the temporary fixing layer deteriorates in the subsequent separation step. Is known. Therefore, it is possible to easily separate the cured resin layer and the temporary fixing layer after forming the cured sealing body with the cured resin layer while applying the cured resin layer as the warpage prevention layer to the cured sealing body. There is a need for a laminate that can be used to produce a cured encapsulant.
  • the present invention has a support layer and a curable resin layer, and can perform sealing by fixing an object to be sealed to the surface of the curable resin layer.
  • a laminated body which can provide a cured resin layer as a warpage preventing layer to a cured sealing body formed by processing, and can easily separate the cured resin layer and the support layer, and the laminated body It is an object of the present invention to provide a method for producing a cured sealing body using the same.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the following problems can be solved by the present invention, and have completed the present invention. That is, the present invention relates to the following [1] to [11].
  • the energy ray-curable resin layer (I) has a surface having tackiness
  • the support layer (II) has a substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles;
  • the storage elastic modulus E ′ at 23 ° C.
  • the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1)
  • the support layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X) in this order,
  • An object to be sealed is placed on a part of the surface of the energy ray-curable resin layer (I), Irradiating the energy ray-curable resin layer (I) with energy rays to form a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I),
  • the object to be sealed and the surface of the cured resin layer (I ') at least in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material, After the sealing material is thermally cured, the cured resin layer (I ′) and the support layer (II) are separated at the interface by a process of expanding the thermally expandable particles, and the object to be sealed is removed.
  • Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by the treatment for expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer.
  • the present invention has a support layer and a curable resin layer, and can perform sealing by fixing an object to be sealed to the surface of the curable resin layer, and can be formed by the sealing.
  • a laminated body that can provide a cured resin layer as a warpage preventing layer to the cured encapsulant, and can easily separate the cured resin layer and the support layer, and curing using the laminated body
  • a method for manufacturing a sealed body can be provided.
  • FIG. 2 is a schematic cross-sectional view of the laminate, showing the configuration of the laminate of the first embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of the laminate showing the configuration of the laminate of the second embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of the laminate showing a configuration of the laminate of the third embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a step of manufacturing a cured sealing body with a cured resin layer using the laminated body 1a shown in FIG. It is a cross-sectional schematic diagram which shows the processing method of a hardened sealing body.
  • a target layer is a “non-expandable layer” is determined by performing a process for expanding for 3 minutes, and then calculating a volume change rate before and after the process based on the following formula. Is less than 5%, it is determined that the layer is a “non-expandable layer”. On the other hand, when the volume change rate is 5% or more, it is determined that the layer is an “expandable layer”.
  • volume change rate (%) ⁇ (volume of the layer after treatment ⁇ volume of the layer before treatment) / volume of the layer before treatment ⁇ ⁇ 100
  • a heat treatment may be performed at the expansion start temperature (t) of the thermally expandable particles for 3 minutes.
  • the “active ingredient” refers to a component excluding a diluting solvent among components contained in a target composition.
  • the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically, a value measured based on the method described in Examples. It is.
  • (meth) acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit and the upper limit described stepwise in a preferable numerical range can be independently combined.
  • a preferable numerical range for example, a range such as the content
  • preferably 10 to 90, more preferably 30 to 60 “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
  • each component and material exemplified in this specification may be used alone, or two or more may be used in combination. When two or more are used in combination, their combination may be used. And the ratio can be arbitrarily selected.
  • the “energy beam” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include an ultraviolet ray, a radiation, and an electron beam.
  • the ultraviolet light can be emitted by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet light source.
  • the electron beam can be emitted from an electron beam generated by an electron beam accelerator or the like.
  • “energy ray-curable” means a property of being cured by irradiation with an energy ray
  • “non-energy ray-curable” means a property of not being cured by irradiation of an energy ray. I do.
  • the laminate of one embodiment of the present invention includes an energy-ray-curable resin layer (I) and a support layer (II) that supports the energy-ray-curable resin layer (I).
  • the energy ray-curable resin layer (I) has an adhesive surface.
  • the support layer (II) has a substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles.
  • the laminate of one embodiment of the present invention comprises a support for curing the energy ray-curable resin layer (I) by curing the heat-expandable particles in the support layer (II) and the cured resin layer (I ′).
  • Layer (II) can be separated at its interface.
  • the heat-expandable particles expand the heat-expandable particles, and the surface of the layer containing the heat-expandable particles has irregularities.
  • the contact area with the cured resin layer (I ′) obtained by curing the conductive resin layer (I) is reduced.
  • the support layer (II) As a result, at the interface between the support layer (II) and the cured resin layer (I ′), it can be easily and collectively separated with a small force.
  • the support layer since the laminate of one embodiment of the present invention does not require heating when curing the energy ray-curable resin layer (I), the support layer is used when the energy ray-curable resin layer (I) is cured.
  • the heat-expandable particles in (II) do not expand, and the separation property between the support layer (II) and the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) is excellent. It will be.
  • an object to be sealed is placed on part of the surface of the energy ray-curable resin layer (I), and the energy ray-curable resin layer (I) is irradiated with energy rays.
  • Is coated with a thermosetting sealing material and after the sealing material is thermoset, the cured resin layer (I ′) and the support layer (II) are expanded by expanding the thermally expandable particles.
  • the cured sealing body formed by the above method has the cured resin layer (I ′) on the surface on the side where the proportion of the semiconductor chips is relatively high.
  • the laminate of one embodiment of the present invention is useful as a laminate for preventing warpage, which is used for preventing warpage of the cured sealing body.
  • the laminate of one embodiment of the present invention includes the energy-ray-curable resin layer (I) which is easily adjusted to increase the adhesive strength more than the thermosetting resin layer, the object to be sealed is part of the surface. Can be fixed more reliably.
  • the thermosetting resin layer is heated at a high temperature, it is softened mainly in an initial stage of curing, which may cause a chip shift. Since it does not soften when cured by irradiation with rays, it is possible to avoid the occurrence of chip deviation due to the curing.
  • FIG. 1 to 3 are schematic cross-sectional views of a laminate showing the configuration of the laminate according to the first to third embodiments of the present invention.
  • the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X) (or the second pressure-sensitive adhesive layer (X2)) to be stuck to the support that is, May be configured such that a release material is further laminated on the surface of the energy ray-curable resin layer (I) opposite to the support layer (II) side.
  • the laminate of the first embodiment of the present invention includes the laminates 1a and 1b shown in FIG.
  • Each of the laminates 1a and 1b includes an energy ray-curable resin layer (I) and a support layer (II) having a substrate (Y) and an adhesive layer (X). It has a configuration in which a linear curable resin layer (I) is directly laminated.
  • the adhesive surface of the adhesive layer (X) is attached to a support (not shown).
  • the support layer (II) contains thermally expandable particles in at least one of the layers, and in the laminate 1a, the base material (Y) is formed of an expandable base material layer containing thermally expandable particles ( This is a base material having a single-layer structure consisting only of Y1).
  • the base material (Y) may be a single-layered base material composed of only the expandable base material layer (Y1) as in a laminate 1a shown in FIG. 1 (a).
  • a base material having a multilayer structure having an expandable base material layer (Y1) and a non-expandable base material layer (Y2) may be used.
  • the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2)
  • the base material (Y) is an expandable base material layer (Y1) and a non-expandable base material layer ( Y2) alone.
  • the expandable base material layer (Y1) and the non-expandable base material layer (Y2) have a configuration in which they are directly laminated.
  • the thermal expansion particles contained in the expandable base material layer (Y1) expand due to the heat expansion treatment, and irregularities are generated on the surface of the base material (Y).
  • the contact area with the cured resin layer (I ′) obtained by previously curing the line-curable resin layer (I) is reduced.
  • the adhesive surface of the adhesive layer (X) is attached to a support (not shown).
  • the surface of the expansible base material layer (Y1) on the side of the pressure-sensitive adhesive layer (X) generates a force to generate irregularities.
  • a repulsive force from the pressure-sensitive adhesive layer (X) is easily generated.
  • the laminate 1a can be easily and collectively separated with a small force at the interface P between the base material (Y) of the support layer (II) and the cured resin layer (I ').
  • the pressure-sensitive adhesive layer (X) of the laminate 1a can be more easily separated at the interface P.
  • the base material (Y) is, as in the laminate 1b shown in FIG. It is preferable to have a material layer (Y1) and a non-expandable base material layer (Y2). Since the stress due to the expansion of the thermally expandable particles of the expandable base material layer (Y1) is suppressed by the non-expandable base material layer (Y2), it is difficult for the stress to be transmitted to the pressure-sensitive adhesive layer (X).
  • the surface of the pressure-sensitive adhesive layer (X) on the support side is unlikely to have irregularities, and the adhesion between the pressure-sensitive adhesive layer (X) and the support hardly changes before and after the heat expansion treatment, and good adhesion is maintained. can do.
  • irregularities are easily formed on the surface of the expandable base material layer (Y1) on the side of the energy ray-curable resin layer (I), and as a result, the support layer (II) and the expandable base material layer (Y1) harden.
  • the support layer (II) and the expandable base material layer (Y1) harden.
  • the interface P with the resin layer (I ′) it is possible to easily and collectively separate them with a small force.
  • the expandable base material layer (Y1) and the energy ray-curable resin layer (I) are directly laminated, and the non-expandable base material layer (Y2) is formed. It is preferable that the pressure-sensitive adhesive layer (X) is laminated on the surface opposite to the expandable base material layer (Y1).
  • the pressure-sensitive adhesive layer (X) of the support layer (II) has a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), and the first pressure-sensitive adhesive layer (X1 ) And the second pressure-sensitive adhesive layer (X2) sandwich the substrate (Y), and the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (X1) is directly laminated with the energy ray-curable resin layer (I).
  • the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown).
  • the substrate (Y) has an expandable substrate layer (Y1) containing thermally expandable particles.
  • the base material (Y) may be a single-layer base material composed of only the expandable base material layer (Y1) as in a laminate 2a shown in FIG. 2 (a).
  • the base material may be a multi-layered base material having an expandable base material layer (Y1) and a non-expandable base material layer (Y2).
  • the material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2).
  • the first pressure-sensitive adhesive layer (X1) is laminated on the surface of the non-expandable base material layer (Y2) on the energy ray-curable resin layer (I) side of the non-expandable base material layer (Y2). It is preferable to have a configuration in which the second pressure-sensitive adhesive layer (X2) is laminated on the surface on the side opposite to (Y1).
  • the thermally expandable particles in the expandable base material layer (Y1) constituting the base material (Y) expand due to the heat expansion treatment, and Irregularities occur.
  • the first adhesive layer (X1) is also pushed up by the unevenness generated on the surface of the expandable base material layer (Y1), and the unevenness is also formed on the adhesive surface of the first adhesive layer (X1).
  • the contact area between the pressure-sensitive adhesive layer (X1) and the cured resin layer (I ′) obtained by previously curing the energy ray-curable resin layer (I) is reduced.
  • the laminate of the second embodiment of the present invention from the viewpoint of making the laminate easily separable at once at the interface P with a smaller force, the expansion of the base material (Y) of the support layer (II) It is preferable that the conductive base material layer (Y1) and the first pressure-sensitive adhesive layer (X1) are directly laminated.
  • the laminate 3 shown in FIG. 3 has a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, on one surface side of a substrate (Y).
  • the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown).
  • the base material (Y) which the laminated body of the 3rd aspect of this invention has is comprised from a non-expandable base material layer.
  • the thermally expandable particles in the first pressure-sensitive adhesive layer (X1) which is the expandable pressure-sensitive adhesive layer, expand due to the heat expansion treatment, and the first pressure-sensitive adhesive layer (X1) Irregularities occur on the surface, and the contact area between the first pressure-sensitive adhesive layer (X1) and the cured resin layer (I ′) obtained by previously curing the energy ray-curable resin layer (I) decreases.
  • the base material (Y) is laminated on the surface of the first pressure-sensitive adhesive layer (X1) on the base material (Y) side, unevenness is unlikely to occur.
  • the heat-expansion treatment tends to form irregularities on the surface of the first pressure-sensitive adhesive layer (X1) on the side of the energy-ray-curable resin layer (I), and as a result, the first pressure-sensitive adhesive layer of the support layer (II) ( At the interface P between the X1) and the cured resin layer (I ′), it can be easily and collectively separated with a small force.
  • the laminate of one embodiment of the present invention may be composed of only the support layer (II) and the energy ray-curable resin layer (I), and the support layer (II) and the energy ray-curable resin layer (I) It may have another layer other than the above.
  • other layers include, for example, an adhesive layer provided on the surface of the energy ray-curable resin layer (I) on the side opposite to the support layer (II).
  • the laminate of one embodiment of the present invention preferably does not include a thermosetting resin layer from the viewpoint that heating is not required as much as possible in steps other than the heat expansion treatment.
  • the thermosetting resin layer here means a layer that has thermosetting properties and is non-energy ray curable.
  • the separation force (F 0 ) at the time of separation at the interface P is preferably 100 mN / 25 mm or more, more preferably 130 mN / 25 mm or more, still more preferably 160 mN / 25 mm or more, and preferably 50,000 mN / 25 mm. It is as follows.
  • the peeling force (F 0 ) is a value measured by the following measuring method. ⁇ Measurement of peeling force (F 0 )> After the laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name “PL Synth”) was applied to the surface of the energy ray-curable resin layer (I).
  • the support layer (II) side of the laminate is attached to a glass plate (float plate glass, 3 mm (JISR 3202 product) manufactured by Yuko Shokai Co., Ltd.) via an adhesive.
  • a glass plate float plate glass, 3 mm (JISR 3202 product) manufactured by Yuko Shokai Co., Ltd.
  • the end of the glass plate to which the laminate is attached is fixed to a lower chuck of a universal tensile tester (manufactured by Orientec Co., Ltd., product name “Tensilon UTM-4-100”).
  • the adhesive tape and the support layer (II) are fixed by the upper chuck of the universal tensile tester so as to be separated at the interface P between the support layer (II) and the energy ray-curable resin layer (I) of the laminate. .
  • peeling force (F 0 ) the peeling force measured when peeling off at the interface P by the 180 ° peeling method at a tensile speed of 300 mm / min based on JIS Z 0237: 2000 is referred to as “peeling force (F 0 ) ".
  • the separation force (F 1 ) at the time of separation at the interface P with the ′) is usually 2000 mN / 25 mm or less, preferably 1000 mN / It is 25 mm or less, more preferably 500 mN / 25 mm or less, more preferably 150 mN / 25 mm or less, further preferably 100 mN / 25 mm or less, even more preferably 50 mN / 25 mm or less, and most preferably 0 mN / 25 mm.
  • the peeling force (F 1 ) is 0 mN / 25 mm, even if an attempt is made to measure the peeling force, it may be impossible to measure because the peeling force is too small.
  • the peeling force (F 1 ) is a value measured by the following measuring method. ⁇ Measurement of peeling force (F 1 )> After the laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name) was applied to the surface of the energy ray-curable resin layer (I) of the laminate. "PL thin") is attached. Next, the support layer (II) side of the laminate is adhered to a glass plate (float plate glass, 3 mm (JIS R 3202), manufactured by Yuko Shokai Co., Ltd.) via an adhesive.
  • a glass plate float plate glass, 3 mm (JIS R 3202), manufactured by Yuko Shokai Co., Ltd.
  • ultraviolet rays are irradiated three times under the conditions of illuminance of 215 mW / cm 2 and light amount of 187 mJ / cm 2 to cure the energy ray-curable resin layer (I) to form a cured resin layer (I ′).
  • the glass plate and the laminate are heated at the maximum expansion temperature for 3 minutes to expand the thermally expandable particles in the expandable base material layer (Y1) of the laminate.
  • the peeling force measured when peeling off at the interface P between the support layer (II) and the cured resin layer (I ′) under the above conditions is determined.
  • peeling force (F 1 ) This is referred to as “peeling force (F 1 )”.
  • peeling force (F 1 ) In the measurement of the peeling force (F 1 ), when the support layer (II) of the laminate was fixed with the upper chuck of the universal tensile tester, the cured resin layer (I ′) was completely separated at the interface P. When fixing is not possible, the measurement is terminated, and the peeling force (F 1 ) at that time is set to “0 mN / 25 mm”.
  • the pressure-sensitive adhesive layer (X) (first pressure-sensitive adhesive layer (X1) and second pressure-sensitive adhesive layer (X2)) of the support layer (II) at room temperature (23 ° C.).
  • the adhesive strength is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, and even more preferably 0.5 to N / 25 mm. ⁇ 4.0 N / 25 mm.
  • the adhesive strength of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is respectively although it is preferable that it is the said range, from a viewpoint of improving the adhesiveness with a support body, and separating easily and collectively at the interface P, the 2nd adhesive layer (X2) of a support body and a 2nd adhesive layer adhered. It is more preferable that the adhesive strength is higher than the adhesive strength of the first adhesive layer (X1).
  • the energy ray-curable resin layer (I) has a surface on which the object to be sealed is placed (that is, The surface opposite to the support layer (II)) has tackiness. Specifically, at room temperature (23 ° C.), the adhesive strength of the surface of the energy ray-curable resin layer (I) on the side on which the object to be sealed is placed is determined from the viewpoint of sufficiently fixing the object to be sealed.
  • the upper limit of the adhesive force of the surface is not particularly limited, but is usually 50 N / 25 mm or less, may be 40 N / 25 mm or less, or may be 30 N / 25 mm or less.
  • these adhesive forces are values measured by the following measuring method.
  • ⁇ Measurement of adhesive strength> A 50 ⁇ m-thick PET film (product name “Cosmoshine A4100”, manufactured by Toyobo Co., Ltd.) is laminated on the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) formed on the release film. Then, the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) is affixed to a stainless steel plate (SUS304 No. 360 polished), which is an adherend, at 23 ° C. and 50% RH (relative humidity). After standing for 24 hours under the environment, the adhesive force at 23 ° C. is measured under the same environment according to JIS Z0237: 2000 by a 180 ° peeling method at a pulling speed of 300 mm / min.
  • the substrate (Y) of the support layer (II) is a non-adhesive substrate.
  • the determination as to whether or not the substrate is a non-adhesive substrate is performed when the probe tack value measured according to JISZ 0237: 1991 with respect to the surface of the target substrate is less than 50 mN / 5 mm ⁇ . If so, the substrate is determined to be a “non-adhesive substrate”. On the other hand, if the probe tack value is 50 mN / 5 mm ⁇ or more, the base material is determined to be “adhesive base material”.
  • the probe tack value on the surface of the substrate (Y) included in the support layer (II) used in one embodiment of the present invention is generally less than 50 mN / 5 mm ⁇ , preferably less than 30 mN / 5 mm ⁇ , and more preferably less than 10 mN / 5 mm ⁇ . , More preferably less than 5 mN / 5 mm ⁇ .
  • the probe tack value on the surface of the substrate (Y) is a value measured by the following measurement method. ⁇ Measurement of probe tack value> A test sample is obtained by cutting a substrate to be measured into a square having a side of 10 mm and leaving it to stand at 23 ° C. and an environment of 50% RH (relative humidity) for 24 hours.
  • the probe tack value on the surface of the test sample was measured using a tacking tester (manufactured by Nippon Tokuseki Co., Ltd., product name “NTS-4800”) according to JIS. It is measured according to Z0237: 1991. Specifically, after a stainless steel probe having a diameter of 5 mm was brought into contact with the surface of the test sample for 1 second at a contact load of 0.98 N / cm 2 , the probe was contacted at a speed of 10 mm / sec. The force required to separate from the surface is measured, and the obtained value is used as the probe tack value of the test sample.
  • the support layer (II) included in the laminate of one embodiment of the present invention includes a base (Y) and an adhesive layer (X), and at least one of the base (Y) and the adhesive layer (X) is provided. It contains thermally expandable particles.
  • the support layer (II) is a layer separated from the energy-ray-curable resin layer (I), which is a support target, by a thermal expansion treatment, and is a layer that plays a role as a so-called temporary fixing layer. .
  • the support layer (II) used in one embodiment of the present invention includes a case where the layer containing the thermally expandable particles is included in the configuration of the base material (Y) and a case where the layer is included in the configuration of the pressure-sensitive adhesive layer (X). Is divided into the following modes. -The support layer (II) of the first embodiment: a support layer (II) including a base material (Y) having an expandable base material layer (Y1) containing thermally expandable particles.
  • the support layer (II) of the second embodiment a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing heat-expandable particles, on both sides of the substrate (Y), and a non-expandable pressure-sensitive adhesive A support layer (II) having a second pressure-sensitive adhesive layer (X2) as a layer.
  • the base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles.
  • the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer, from the viewpoint of easily and collectively separating at a small force at the interface P.
  • the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer.
  • both the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are non-expandable pressure-sensitive adhesive layers.
  • the pressure-sensitive adhesive layer (X) since the base material (Y) has the expandable base material layer (Y1), the pressure-sensitive adhesive layer (X) does not need to have the expandability, and the expandability is reduced. It is not restricted by the composition, composition and process for application. In this way, when designing the pressure-sensitive adhesive layer (X), for example, it is possible to perform a design that prioritizes desired performance other than expandability such as performance such as adhesiveness, productivity, economy, and the like. (X) The design flexibility can be improved.
  • the thickness of the substrate (Y) of the support layer (II) of the first embodiment before the heat expansion treatment is preferably from 10 to 1000 ⁇ m, more preferably from 20 to 700 ⁇ m, further preferably from 25 to 500 ⁇ m, and still more preferably from 30 to 30 ⁇ m. 300300 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (X) of the support layer (II) of the first embodiment before the heat expansion treatment is preferably 1 to 60 ⁇ m, more preferably 2 to 50 ⁇ m, still more preferably 3 to 40 ⁇ m, and still more preferably. It is 5 to 30 ⁇ m.
  • the “thickness of the pressure-sensitive adhesive layer (X)” It means the thickness of each pressure-sensitive adhesive layer (in FIG. 2, each thickness of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2)). Further, in the present specification, the thickness of each layer constituting the laminate means a value measured by the method described in Examples.
  • the thickness ratio [(Y1) / (X)] between the expandable base material layer (Y1) and the pressure-sensitive adhesive layer (X) before the heat expansion treatment is as follows. It is preferably at most 1,000, more preferably at most 200, further preferably at most 60, even more preferably at most 30. When the thickness ratio is 1000 or less, a laminate that can be easily and collectively separated with a small force at the interface P between the support layer (II) and the cured resin layer (I ′) by the heat expansion treatment is provided. can do.
  • the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1.0 or more, and still more preferably 5.0 or more.
  • the base material (Y) may be composed of only the expandable base material layer (Y1) as shown in FIG. As shown in FIG. 1 (b), it has an expandable base material layer (Y1) on the energy ray-curable resin layer (I) side and a non-expandable base material layer (Y2) on the adhesive layer (X) side. May be provided.
  • the thickness ratio [(Y1) / (Y2)] between the expandable base material layer (Y1) and the non-expandable base material layer (Y2) before the heat expansion treatment is preferably 0.02 to 200, more preferably 0.03 to 150, and still more preferably 0.05 to 100.
  • a first pressure-sensitive adhesive layer which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, is provided on both sides of the substrate (Y).
  • the first pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer, and the energy ray-curable resin layer (I) are in direct contact.
  • the substrate (Y) is preferably a non-expandable substrate. It is preferable that the non-expandable base material is composed of only the non-expandable base material layer (Y2).
  • the first pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer before the heat expansion treatment.
  • the thickness ratio ((X1) / (X2)) is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.
  • the thickness ratio of the first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer, to the base material (Y) before the heat expansion treatment [(X1) / (Y)] is preferably from 0.05 to 20, more preferably from 0.1 to 10, and even more preferably from 0.2 to 3.
  • the expansible base material layer (Y1) constituting the base material (Y) and the non-expandable base material The layer (Y2) and the pressure-sensitive adhesive layer (X) will be described in detail.
  • Thermally expandable particles As the heat-expandable particles used in one embodiment of the present invention, any particles may be used as long as they are expanded by a predetermined heat expansion process.
  • the average particle size of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, further preferably 6 to 60 ⁇ m, and still more preferably 10 to 100 ⁇ m. 50 ⁇ m.
  • the average particle diameter of the thermally expandable particles before expansion is a volume median particle diameter (D 50 ), and is a laser diffraction particle size distribution analyzer (for example, product name “Master Sizer 3000” manufactured by Malvern).
  • the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion corresponds to a particle size corresponding to 50%.
  • the 90% particle diameter (D 90 ) of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 25 to 90 ⁇ m. Even more preferably, it is 30 to 80 ⁇ m.
  • the 90% particle diameter (D 90 ) of the thermally expandable particles before expansion is measured using a laser diffraction type particle size distribution analyzer (for example, product name “Master Sizer 3000” manufactured by Malvern). In the particle distribution of the heat-expandable particles before, it means a particle diameter whose cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion corresponds to 90%.
  • the thermally expandable particles used in one embodiment of the present invention may be particles that do not expand when the sealing material is cured and have an expansion start temperature (t) higher than the curing temperature of the sealing material. It is preferable that the thermal expansion particles have an expansion start temperature (t) adjusted to 60 to 270 ° C.
  • the expansion start temperature (t) is appropriately selected according to the curing temperature of the sealing material to be used. Further, in the present specification, the expansion start temperature (t) of the thermally expandable particles means a value measured based on the method described in Examples.
  • a microencapsulated foaming agent comprising an outer shell made of a thermoplastic resin, and an inner component contained in the outer shell and vaporized when heated to a predetermined temperature.
  • the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include a vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
  • Examples of the internal components included in the outer shell include, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane , Cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, isotridecane, 4-methyldodecane, isote
  • the maximum volume expansion coefficient of the heat-expandable particles used in one embodiment of the present invention when heated to a temperature equal to or higher than the expansion start temperature (t) is preferably 1.5 to 100 times, more preferably 2 to 80 times, and furthermore Preferably it is 2.5 to 60 times, more preferably 3 to 40 times.
  • the expandable base material layer (Y1) included in the support layer (II) used in one embodiment of the present invention is a layer that contains thermally expandable particles and can be expanded by a predetermined heat expansion treatment.
  • the surface of the expandable base material layer (Y1) is oxidized, surface-roughened, or the like.
  • Treatment, easy adhesion treatment, or primer treatment may be performed.
  • the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet method), hot air treatment, ozone, and ultraviolet irradiation treatment.
  • the unevenness method include a sand blast method and a solvent treatment method. And the like.
  • the expandable base material layer (Y1) preferably satisfies the following requirement (1).
  • the storage elastic modulus E '(t) of the expandable base material layer (Y1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 ⁇ 10 7 Pa or less.
  • the storage elastic modulus E ′ of the expandable base material layer (Y1) at a predetermined temperature means a value measured by the method described in Examples.
  • the requirement (1) can be said to be an index indicating the rigidity of the expandable base material layer (Y1) immediately before the expansion of the thermally expandable particles.
  • the support layer It is necessary to make it easy to form irregularities on the surface on the side laminated with the energy ray-curable resin layer (I) of (II).
  • the thermally expandable particles expand at the expansion start temperature (t) and become sufficiently large, and the energy ray-curable resin layer (I) is Irregularities are likely to be formed on the surface of the support layer (II) on the side where the coating is formed.
  • a laminate that can be easily separated with a small force at the interface P between the support layer (II) and the cured resin layer (I ′) can be obtained.
  • the storage elastic modulus E ′ (t) of the expandable base material layer (Y1) defined by the requirement (1) is preferably 9.0 ⁇ 10 6 Pa or less, more preferably 8.0 ⁇ 10 6 Pa. 6 Pa or less, more preferably 6.0 ⁇ 10 6 Pa or less, and even more preferably 4.0 ⁇ 10 6 Pa or less.
  • the storage elastic modulus E ′ (t) of the expandable base material layer (Y1) which is defined in the requirement (1), is preferably 1.0 ⁇ . It is at least 10 3 Pa, more preferably at least 1.0 ⁇ 10 4 Pa, even more preferably at least 1.0 ⁇ 10 5 Pa.
  • the expandable base material layer (Y1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.
  • the resin composition (y) may contain an additive for a base material, if necessary, as long as the effects of the present invention are not impaired.
  • the base material additive include a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, and the like.
  • these additives for base materials may be used independently, respectively, and may use 2 or more types together.
  • the content of each base material additive is preferably from 0.0001 to 20 parts by mass, more preferably from 0.001 to 20 parts by mass, based on 100 parts by mass of the resin. 10 parts by mass.
  • the content of the thermally expandable particles is preferably 1 to 40 with respect to the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the active ingredient of the resin composition (y). %, More preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass.
  • the resin contained in the resin composition (y) that is the material for forming the expandable base material layer (Y1) may be a non-adhesive resin or an adhesive resin. That is, even if the resin contained in the resin composition (y) is an adhesive resin, in the process of forming the expandable base material layer (Y1) from the resin composition (y), the adhesive resin becomes polymerizable. It suffices that the resin obtained by a polymerization reaction with the compound becomes a non-adhesive resin and the expandable base material layer (Y1) containing the resin becomes non-adhesive.
  • the weight average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 700,000, and further preferably from 1,000 to 500,000.
  • the form of the copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer. It may be.
  • the content of the resin is preferably 50 to 99% by mass based on the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount of the active ingredients (100% by mass) of the resin composition (y). , More preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.
  • the resin contained in the resin composition (y) is selected from acrylic urethane-based resins and olefin-based resins. Preferably, it contains more than one species.
  • the following resin (U1) is preferable as the acrylic urethane-based resin. -An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylate.
  • urethane prepolymer (UP) serving as the main chain of the acrylic urethane-based resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
  • the urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.
  • Examples of the polyol serving as a raw material of the urethane prepolymer (UP) include an alkylene type polyol, an ether type polyol, an ester type polyol, an ester amide type polyol, an ester ether type polyol, and a carbonate type polyol. These polyols may be used alone or in combination of two or more.
  • the polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, or a carbonate diol, and further preferably an ester diol or a carbonate diol.
  • ester type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; and phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, and diphenylmethane-4 , 4'-Dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, heptic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4
  • alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, Alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol;
  • Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. , 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol and the like.
  • polyvalent isocyanate serving as a raw material of the urethane prepolymer (UP)
  • examples of the polyvalent isocyanate serving as a raw material of the urethane prepolymer (UP) include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate. These polyvalent isocyanates may be used alone or in combination of two or more. In addition, these polyvalent isocyanates may be a modified trimethylolpropane adduct, a modified buret reacted with water, or a modified isocyanurate containing an isocyanurate ring.
  • diisocyanate is preferable, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 One or more selected from -tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate are more preferable.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • HMDI hexamethylene diisocyanate
  • alicyclic diisocyanate are more preferable.
  • alicyclic diisocyanate examples include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane
  • IPDI isophorone diisocyanate
  • diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate isophorone diisocyanate (IPDI) is preferable.
  • the urethane prepolymer (UP) serving as the main chain of the acrylic urethane-based resin (U1) is a reaction product of a diol and a diisocyanate, and has a straight chain having an ethylenically unsaturated group at both terminals.
  • Urethane prepolymers are preferred.
  • a NCO group at a terminal of the linear urethane prepolymer obtained by reacting a diol with a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
  • the vinyl compound serving as a side chain of the acrylic urethane resin (U1) contains at least a (meth) acrylate.
  • the (meth) acrylic acid ester one or more selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are preferable, and it is more preferable to use the alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate together.
  • the mixing ratio of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 100 parts by mass. Preferably it is 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, even more preferably 1.5 to 10 parts by mass.
  • the alkyl group of the alkyl (meth) acrylate preferably has 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 3.
  • hydroxyalkyl (meth) acrylate the same hydroxyalkyl (meth) acrylate used to introduce an ethylenically unsaturated group into both terminals of the above-mentioned linear urethane prepolymer can be used.
  • vinyl compounds other than (meth) acrylic acid esters include, for example, aromatic hydrocarbon-based vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate , (Meth) acrylonitrile, N-vinylpyrrolidone, polar group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and meth (acrylamide). These may be used alone or in combination of two or more.
  • the content of the (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.
  • the total content of the alkyl (meth) acrylate and the hydroxyalkyl (meth) acrylate in the vinyl compound is preferably from 40 to 100% by mass, more preferably from 65 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound. It is 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass.
  • the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 ) / (U12)] is preferably from 10/90 to 80/20, more preferably from 20/80 to 70/30, still more preferably from 30/70 to 60/40, and even more preferably 35 by mass ratio. / 65 to 55/45.
  • the olefin-based resin suitable as the resin contained in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
  • the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and specific examples include ethylene, propylene, butylene, isobutylene, 1-hexene and the like. Among these, ethylene and propylene are preferred.
  • olefinic resins for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m less than 3 ), medium density polyethylene (MDPE, density: 915 kg / m 3 or more 942kg / m less than 3), high density polyethylene (HDPE, density: 942kg / m 3 or higher), polyethylene resins such as linear low density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin-based elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefin terpolymers such as-(5-ethylidene-2-n
  • the olefin-based resin may be a modified olefin-based resin further subjected to at least one modification selected from acid modification, hydroxyl group modification, and acrylic modification.
  • the acid-modified olefin resin obtained by subjecting the olefin resin to acid modification a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof with the above-mentioned unmodified olefin resin. Is mentioned.
  • Examples of the above unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, and itaconic anhydride , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like.
  • the unsaturated carboxylic acids or their anhydrides may be used alone or in combination of two or more.
  • the acrylic-modified olefin-based resin obtained by subjecting the olefin-based resin to an acrylic modification is a modified olefin-based resin obtained by graft-polymerizing an alkyl (meth) acrylate as a side chain to the unmodified olefin-based resin as a main chain.
  • the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12.
  • Examples of the above-mentioned alkyl (meth) acrylate include the same compounds as the compounds that can be selected as the monomer (a1 ′) described below.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting the olefin resin to hydroxyl group modification include a modified polymer obtained by graft-polymerizing a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin as a main chain.
  • Examples of the hydroxyl-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl.
  • Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • the resin composition (y) may contain a resin other than the acrylic urethane resin and the olefin resin, as long as the effects of the present invention are not impaired.
  • resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; and acrylonitrile-butadiene-styrene copolymer.
  • Polycarbonate Polyether ether ketone; Polyether sulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorinated resins and the like can be mentioned.
  • the content ratio of the resin other than the acrylic urethane resin and the olefin resin is preferably less than 30 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than 10 parts by weight, more preferably less than 5 parts by weight, even more preferably less than 1 part by weight.
  • solvent-free resin composition (y1) As the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray-polymerizable monomer, and the above-described thermally expandable particles are blended. And a solvent-free resin composition (y1) containing no solvent. In the solventless resin composition (y1), no solvent is blended, but the energy ray polymerizable monomer contributes to the improvement of the plasticity of the oligomer. By irradiating the coating film formed from the solvent-free resin composition (y1) with an energy ray, it is easy to form the expandable base material layer (Y1) satisfying the requirement (1).
  • Mw mass average molecular weight
  • the type, shape and blending amount (content) of the thermally expandable particles blended in the solventless resin composition (y1) are as described above.
  • the weight average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and still more preferably 3,000 to 35,000, Still more preferably, it is 4000 to 30,000.
  • the oligomer may be any of the resins contained in the resin composition (y) described above, as long as the resin has an ethylenically unsaturated group having a weight average molecular weight of 50,000 or less. UP) is preferred.
  • a modified olefin-based resin having an ethylenically unsaturated group may be used as the oligomer.
  • the total content of the oligomer and the energy ray-polymerizable monomer in the solventless resin composition (y1) is preferably 50 to 50% based on the total amount (100% by mass) of the solventless resin composition (y1). It is 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, even more preferably 70 to 85% by mass.
  • Examples of the energy beam polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, and adamantane ( Alicyclic polymerizable compounds such as meth) acrylate and tricyclodecane acrylate; aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol-ethylene oxide modified acrylate; tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- Heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. These energy ray polymerizable monomers may be used alone or in combination of two or more.
  • the mixing ratio of the oligomer and the energy ray-polymerizable monomer is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, and still more preferably 35/65. 8080/20.
  • the solvent-free resin composition (y1) preferably further contains a photopolymerization initiator.
  • the curing reaction can be sufficiently advanced even by irradiation with relatively low energy energy rays.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol Examples include nitrile, dibenzyl, diacetyl, 8-chloranthraquinone and the like. These photopolymerization initiators may be used alone or in combination of two or more.
  • the compounding amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, based on the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer. Preferably it is 0.02 to 3 parts by mass.
  • Non-expandable base material layer (Y2) As a material for forming the non-expandable base material layer (Y2) included in the base material (Y), for example, a paper material, a resin, a metal, or the like can be given. You can choose.
  • Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, parchment paper, glassine paper, and the like.
  • Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer; polyethylene terephthalate, Polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polysulfone; Polyether sulfone; Polyphenylene sulfide; Polyimide-based resin such as polyetherimide and polyimide;
  • these forming materials may be composed of one type, or two or more types may be used in combination.
  • a method of forming the metal layer for example, a method in which the metal is deposited by a PVD method such as vacuum evaporation, sputtering, or ion plating, or a metal foil made of the metal is attached using a general adhesive. And the like.
  • the expandable base material layer (Y1) when the expandable particles contained in the expandable base material layer (Y1) expand, the expandable base material layer (Y1) is closer to the non-expandable base material layer (Y2).
  • the non-expandable base material layer ( Y2) preferably has such a rigidity that it does not deform due to expansion of the expandable particles.
  • the storage elastic modulus E ′ (t) of the non-expandable base material layer (Y2) at the temperature (t) at the time when the expansion of the expandable particles starts is 1.1 ⁇ 10 7 Pa or more. Is preferred.
  • the non-expandable base material layer (Y2) contains a resin
  • the non-expandable base material layer (Y2) may be subjected to a surface treatment such as an oxidation method or a concavo-convex method, an easy adhesion treatment, or a primer treatment as in the case of the above-described expandable base material layer (Y1).
  • the non-expandable base material layer (Y2) contains a resin
  • the above-mentioned base material additive which may be contained in the resin composition (y) may be contained together with the resin.
  • the non-intumescent base material layer (Y2) is a non-intumescent layer determined based on the method described above. Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) calculated from the above equation is less than 5%, preferably less than 2%, more preferably less than 1%, and still more preferably. Is less than 0.1%, even more preferably less than 0.01%.
  • the non-expandable base material layer (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range.
  • the non-expandable base material layer (Y2) does not contain thermally expandable particles.
  • the content thereof is preferably as small as possible.
  • the pressure-sensitive adhesive layer (X) included in the support layer (II) used in one embodiment of the present invention can be formed from a pressure-sensitive adhesive composition (x) containing a pressure-sensitive adhesive resin. Further, the pressure-sensitive adhesive composition (x) may contain a pressure-sensitive adhesive additive such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
  • a pressure-sensitive adhesive additive such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
  • the support layer (II) has the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2)
  • the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are also
  • the pressure-sensitive adhesive composition (x) containing the following components.
  • the pressure-sensitive adhesive resin used in one embodiment of the present invention is preferably a polymer having the pressure-sensitive adhesive alone and having a weight average molecular weight (Mw) of 10,000 or more.
  • the weight average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1.5,000,000, and still more preferably 30,000, from the viewpoint of improving the adhesive strength. ⁇ 1 million.
  • Specific adhesive resins include, for example, rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. These adhesive resins may be used alone or in combination of two or more. When these adhesive resins are copolymers having two or more types of constituent units, the form of the copolymer is not particularly limited, and may be a block copolymer, a random copolymer, or a graft copolymer. Any of polymers may be used.
  • the adhesive resin preferably contains an acrylic resin from the viewpoint of developing excellent adhesive strength.
  • the first pressure-sensitive adhesive layer By including an acrylic resin in X1), it is possible to easily form irregularities on the surface of the first pressure-sensitive adhesive layer (X1).
  • the content of the acrylic resin in the adhesive resin is preferably 30 to 30% based on the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X). It is 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
  • the content of the pressure-sensitive adhesive resin is preferably 35 to 100% by mass relative to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X). %, More preferably 50 to 100% by mass, still more preferably 60 to 98% by mass, and still more preferably 70 to 95% by mass.
  • the pressure-sensitive adhesive composition (x) when the pressure-sensitive adhesive composition (x) contains a pressure-sensitive adhesive resin having a functional group, the pressure-sensitive adhesive composition (x) preferably further contains a crosslinking agent.
  • the crosslinking agent reacts with the adhesive resin having a functional group, and crosslinks the adhesive resins with the functional group as a crosslinking starting point.
  • crosslinking agent examples include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, and a metal chelate-based crosslinking agent. These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoint of increasing the cohesive force to improve the adhesive strength and from the viewpoint of easy availability.
  • the content of the crosslinking agent is appropriately adjusted depending on the number of functional groups contained in the adhesive resin, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group. More preferably, it is 0.03 to 7 parts by mass, and still more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (x) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
  • the “tackifier” is a component that assists in improving the adhesive strength of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, It is distinguished from the conductive resin.
  • the weight average molecular weight (Mw) of the tackifier is preferably 400 to 9000, more preferably 500 to 8000, and further preferably 800 to 5000.
  • tackifier examples include rosin-based resins, terpene-based resins, styrene-based resins, and copolymers of C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene generated by thermal decomposition of petroleum naphtha.
  • C5 petroleum resin obtained a C9 petroleum resin obtained by copolymerizing a C9 fraction such as indene and vinyltoluene generated by thermal decomposition of petroleum naphtha, and a hydrogenated resin obtained by hydrogenating these.
  • the softening point of the tackifier is preferably from 60 to 170 ° C, more preferably from 65 to 160 ° C, and even more preferably from 70 to 150 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K 2531.
  • the tackifier may be used alone, or two or more kinds having different softening points and structures may be used in combination. When two or more tackifiers are used, the weighted average of the softening points of the tackifiers preferably falls within the above range.
  • the content of the tackifier is preferably 0.01 to 65% based on the total amount of the active ingredient (100% by mass) of the pressure-sensitive adhesive composition (x) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X). %, More preferably 0.1 to 50% by mass, still more preferably 1 to 40% by mass, and still more preferably 2 to 30% by mass.
  • the pressure-sensitive adhesive composition (x) contains a pressure-sensitive adhesive additive used for a general pressure-sensitive adhesive, in addition to the additives described above, as long as the effects of the present invention are not impaired. It may be.
  • adhesive additives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, and the like. Is mentioned.
  • These pressure-sensitive adhesive additives may be used alone or in combination of two or more. When these adhesive additives are contained, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 20 parts by mass, based on 100 parts by mass of the adhesive resin. 1010 parts by mass.
  • the first pressure-sensitive adhesive layer (X1) that is the expandable pressure-sensitive adhesive layer is used.
  • the forming material is formed from the expandable pressure-sensitive adhesive composition (x11) further containing the heat-expandable particles in the pressure-sensitive adhesive composition (x) described above.
  • the thermally expandable particles are as described above.
  • the content of the heat-expandable particles is preferably 1 to 100% based on the total amount of the active ingredient (100% by mass) or the total amount (100% by mass) of the expandable pressure-sensitive adhesive composition (x11). It is 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass.
  • the pressure-sensitive adhesive composition (x) which is a material for forming the non-expandable pressure-sensitive adhesive layer, preferably does not contain thermally expandable particles.
  • the content is preferably as small as possible.
  • the content is preferably based on the total amount of active ingredients (100% by mass) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive composition (x). On the other hand, it is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass.
  • a support layer (II) having a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), which is a non-expandable pressure-sensitive adhesive layer, is used as in the laminates 2a and 2b shown in FIG.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 ⁇ 10 8 Pa or less, more preferably 5.0 ⁇ 10 8 Pa or less.
  • the pressure is 0 ⁇ 10 7 Pa or less, more preferably 1.0 ⁇ 10 7 Pa or less.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1) which is a non-expandable pressure-sensitive adhesive layer, is 1.0 ⁇ 10 8 Pa or less, for example, the laminates 2a and 2b shown in FIG.
  • the first pressure-sensitive adhesive layer (X1) in contact with the cured resin layer (I ′) due to the expansion of the thermally expandable particles in the expandable base material layer (Y1) due to the heat expansion treatment. ) Is likely to form irregularities on the surface.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 ⁇ 10 4 Pa or more, and more preferably 5.10 ⁇ 10 4 Pa or more. 0 ⁇ 10 4 Pa or more, more preferably 1.0 ⁇ 10 5 Pa or more.
  • the light transmittance at a wavelength of 375 nm of the support layer (II) included in the laminate of one embodiment of the present invention is preferably 30% or more, more preferably 50% or more, and still more preferably 70% or more.
  • the degree is more improved.
  • the upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, but can be, for example, 95% or less.
  • the transmittance can be measured according to a known method using a spectrophotometer.
  • the effect of the present invention is not impaired. It is preferable to adjust the content.
  • the content is preferably as small as possible.
  • the content is based on the total amount of the active ingredient (100% by mass) or the total amount of the pressure-sensitive adhesive layer (X) (100% by mass). , Preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, even more preferably less than 0.001% by mass.
  • the content of the coloring agent is preferably less than 1% by mass, more preferably less than 1% by mass, based on the total amount (100% by mass) of the active ingredients of the resin composition (y) or the total amount (100% by mass) of the base material (Y). It is less than 0.1% by mass, more preferably less than 0.01% by mass, even more preferably less than 0.001% by mass.
  • the energy ray-curable resin layer (I) is not particularly limited as long as it is a layer that can be cured by irradiating an energy ray.
  • the energy ray-curable resin composition containing the energy ray-curable component (a) Is formed.
  • the energy ray-curable component (a) is a component that is cured by irradiation with energy rays.
  • the energy ray-curable component (a) a polymer (a1) having an energy ray-curable double bond and having a mass average molecular weight (Mw) of 80,000 to 2,000,000 (hereinafter, also simply referred to as “polymer (a1)”)
  • a compound (a2) having an energy-ray-curable double bond and a molecular weight of 100 to 80,000 hereinafter also simply referred to as “compound (a2)”.
  • the energy ray-curable component (a) may be used alone or in combination of two or more.
  • the polymer (a1) is a polymer having an energy ray-curable double bond and having a weight average molecular weight (Mw) of 80,000 to 2,000,000.
  • Examples of the polymer (a1) include an acrylic polymer (a11) having a functional group X capable of reacting with a group of another compound, a group Y reacting with the functional group X, and an energy ray-curable double.
  • An acrylic resin (a1-1) obtained by polymerizing the energy ray-curable compound (a12) having a bond and the polymer is exemplified.
  • the polymer (a1) may be used alone or in combination of two or more.
  • Acrylic polymer (a11) examples include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom. Or an epoxy group.
  • acrylic polymer (a11) examples include those obtained by copolymerizing an acrylic monomer having the functional group X and an acrylic monomer having no functional group X. Further, a monomer (non-acrylic monomer) other than the acrylic monomer may be copolymerized.
  • the acrylic polymer (a11) may be a random copolymer or a block copolymer. The acrylic polymer (a11) may be used alone or in combination of two or more.
  • Examples of the acrylic monomer having the functional group X include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
  • Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid.
  • Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturated compounds such as vinyl alcohol and allyl alcohol Alcohol (unsaturated alcohol having no (meth) acryloyl skeleton) and the like.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citraconic acid Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate. .
  • a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.
  • acrylic monomer having no functional group X examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid.
  • n-butyl isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pent
  • acrylic monomer having no functional group X examples include, for example, methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like.
  • (Meth) acrylic acid esters having an aromatic group including (meth) acrylic acid esters containing an alkoxyalkyl group of the following; aryl (meth) acrylic acid esters such as phenyl (meth) acrylate; non-crosslinkable (meth) Acrylamide and its derivatives; (meth) acrylates having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; No.
  • the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
  • the content of the structural unit derived from the acrylic monomer having the functional group X is preferably from 0.1 to 50% by mass, based on the total amount of the structural units constituting the polymer. Preferably it is 1 to 40% by mass, more preferably 3 to 30% by mass.
  • the content of the structural unit is within the above range, the content of the energy ray-curable double bond in the obtained acrylic resin (a1-1) can be easily adjusted to a preferable range.
  • the energy ray-curable compound (a12) is a compound having a group Y that reacts with the functional group X and an energy ray-curable double bond.
  • the group Y include one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group, and among these, an isocyanate group is preferable.
  • the energy ray-curable compound (a12) has an isocyanate group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
  • the number of energy beam-curable double bonds contained in the energy beam-curable compound (a12) is preferably 1 to 5, more preferably 1 to 3, in one molecule.
  • the energy ray-curable compound (a12) may be used alone or in combination of two or more.
  • Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meth-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate and 1,1- (bisacryloyloxymethyl) ethyl Isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth) acrylate Acryloyl monoisocyanate compound.
  • 2-methacryloyloxyethyl isocyanate is preferred.
  • the content of the energy ray-curable double bond derived from the energy ray-curable compound (a12) relative to the content of the functional group X derived from the acrylic polymer (a11) Is preferably 20 to 120 mol%, more preferably 5 to 100 mol%, and still more preferably 50 to 100 mol%.
  • the adhesive strength of the cured resin layer (I ′) formed by curing becomes larger.
  • the energy ray-curable compound (a12) is a monofunctional compound (having one of the above groups in one molecule)
  • the upper limit of the content is 100 mol%.
  • the curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule)
  • the upper limit of the content may exceed 100 mol%.
  • the content of the acrylic resin (a1-1) is based on the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , Preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and still more preferably 3 to 20% by mass.
  • the weight average molecular weight (Mw) of the polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1500,000.
  • the polymer (a1) may be at least partially cross-linked by a cross-linking agent (e) described below, or may be non-cross-linked.
  • Compound (a2) is a compound having an energy ray-curable double bond and a molecular weight of 100 to 80,000.
  • As the energy ray-curable double bond of the compound (a2) a (meth) acryloyl group, a vinyl group and the like are preferable.
  • Examples of the compound (a2) include a low molecular weight compound having an energy ray-curable double bond, an epoxy resin having an energy ray-curable double bond, and a phenol resin having an energy ray-curable double bond. .
  • the compound (a2) may be used alone or in combination of two or more.
  • Examples of the low molecular weight compound having an energy ray-curable double bond include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
  • Examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4- ((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecan
  • epoxy resin having an energy-ray-curable double bond and the phenol resin having an energy-ray-curable double bond for example, those described in paragraph 0043 of JP-A-2013-194102 are used. be able to.
  • a resin also corresponds to a resin constituting the thermosetting component (f) described later, but is handled as the compound (a2) in the present invention.
  • the mass average molecular weight (Mw) of the compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.
  • the content of the compound (a2) is preferably 1% with respect to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). It is preferably from 40 to 40% by mass, more preferably from 2 to 30% by mass, and still more preferably from 3 to 20% by mass.
  • the energy ray-curable resin composition contains the compound (a2)
  • the energy ray-curable resin composition further contains a polymer (b) having no energy ray-curable double bond (hereinafter, also simply referred to as “polymer (b)”). Is preferred.
  • the polymer (b) may be used alone or in combination of two or more.
  • polymer (b) examples include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, an acrylic urethane resin, polyvinyl alcohol (PVA), a butyral resin, and a polyester urethane resin.
  • an acrylic polymer hereinafter, also referred to as “acrylic polymer (b-1)” is preferable.
  • the acrylic polymer (b-1) may be a known one.
  • it may be a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers.
  • it may be a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).
  • acrylic monomer constituting the acrylic polymer (b-1) examples include: (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, and hydroxyl group (Meth) acrylic acid esters, substituted amino group-containing (meth) acrylic acid esters, and the like.
  • the “substituted amino group” is as described above.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • Examples of the (meth) acrylate having a cyclic skeleton include, for example, cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; benzyl (meth) acrylate and the like.
  • Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate.
  • Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
  • Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate.
  • non-acrylic monomer constituting the acrylic polymer (b-1) examples include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
  • the polymer (b) may be at least partially cross-linked by the cross-linking agent (e), or may be non-cross-linked.
  • the polymer (b) at least partially crosslinked by the crosslinking agent (e) includes, for example, a polymer in which a reactive functional group in the polymer (b) has reacted with the crosslinking agent (e).
  • the reactive functional group may be appropriately selected according to the type of the crosslinking agent (e) and the like, and is not particularly limited.
  • the crosslinking agent (e) is a polyisocyanate compound
  • examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. High hydroxyl groups are preferred.
  • the reactive functional group includes, for example, a carboxy group, an amino group, an amide group and the like. Are preferred. However, it is preferable that the reactive functional group be a group other than a carboxy group from the viewpoint of preventing corrosion of circuits of the semiconductor wafer and the semiconductor chip.
  • the polymer (b) having the reactive functional group for example, a polymer obtained by polymerizing at least the monomer having the reactive functional group can be mentioned.
  • the acrylic polymer (b-1) any one or both of the acrylic monomer and the non-acrylic monomer described above as the monomer constituting the acrylic polymer (b-1) having the reactive functional group is used. It may be used.
  • the polymer (b) having a hydroxyl group as a reactive functional group for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester may be mentioned.
  • acrylic monomers or non-acrylic monomers there may be mentioned those obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional group.
  • the content of the structural unit derived from the monomer having a reactive functional group is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, based on the total amount of the structural units constituting the polymer (b). is there.
  • the degree of crosslinking in the polymer (b) is in a more preferable range.
  • the mass average molecular weight (Mw) of the polymer (b) is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1500,000, from the viewpoint that the film formability of the energy ray-curable resin composition becomes better.
  • Examples of the energy ray-curable resin composition include those containing one or both of the polymer (a1) and the compound (a2).
  • the resin composition contains the compound (a2)
  • the polymer (b) is also used. It is preferred to contain.
  • the total content of the energy ray-curable component (a) and the polymer (b) is determined based on the total amount of the active components (100% by mass) of the energy ray-curable resin composition or the total amount of the energy ray-curable resin layer (I) ( 100% by mass), preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass. When the total content is within the above range, the energy ray curability becomes better.
  • the content of the polymer (b) is The amount is preferably from 3 to 160 parts by mass, more preferably from 6 to 130 parts by mass, based on 100 parts by mass of the active ingredient (a).
  • the content of the polymer (b) is in the above range, the energy ray curability becomes better.
  • the energy ray-curable resin composition contains, in addition to the energy ray-curable component (a) and the polymer (b), a photopolymerization initiator (c), a coupling agent (d), and a crosslinking agent (e) according to the purpose. ), A coloring agent (g), a thermosetting component (f), a curing accelerator (g), a filler (h) and a general-purpose additive (z). Is also good.
  • the formed energy-ray-curable resin layer (I) is coated by heating. The adhesive strength to the adherend is improved, and the strength of the cured resin layer (I ′) formed from the energy ray-curable resin layer (I) is also improved.
  • Photopolymerization initiator (c) examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; Acetophenone compounds such as -hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide ⁇ -ketol compounds such as 1-hydroxycyclohexylphenyl
  • a quinone compound such as 1-chloroanthraquinone
  • a photosensitizer such as an amine
  • the photopolymerization initiator (c) may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (c) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is preferably 0.1 to 100 parts by mass of the energy ray-curable compound (a).
  • the amount is from 01 to 20 parts by mass, preferably from 0.03 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass.
  • Coupleling agent (d) By using a coupling agent (d) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness of the energy ray-curable resin layer (I) can be improved.
  • the cured resin layer (I ') obtained by curing the curable resin layer (I) has improved water resistance without impairing the heat resistance.
  • the coupling agent (d) may be used alone or in combination of two or more.
  • the coupling agent (d) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray-curable component (a), the polymer (b) or the like, and is preferably a silane coupling agent. More preferred.
  • silane coupling agent examples include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino ) Propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-
  • the content of the coupling agent (d) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is 100 parts by mass in total of the energy ray-curable component (a) and the polymer (b). On the other hand, it is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass.
  • the content of the coupling agent (d) is equal to or more than the above lower limit, effects such as improvement in dispersibility of the filler in the resin and improvement in adhesiveness of the energy ray-curable resin layer (I) are more remarkably obtained.
  • the generation of outgas is suppressed by being equal to or less than the upper limit.
  • Crosslinking agent (e) By cross-linking the energy ray-curable component (a), the polymer (b), and the like using the cross-linking agent (e), the initial adhesive strength and cohesion of the energy ray-curable resin layer (I) can be adjusted.
  • the crosslinking agent (e) may be used alone or in combination of two or more.
  • crosslinking agent (e) examples include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based crosslinker (a crosslinker having a metal chelate structure), an aziridine-based crosslinker (a crosslinker having an aziridinyl group), and the like. Is mentioned.
  • organic polyvalent isocyanate compound examples include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively abbreviated as “aromatic polyvalent isocyanate compound, etc.”). Trimers, isocyanurates and adducts of the aromatic polyisocyanate compound, etc .; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compound with a polyol compound, etc. Is mentioned.
  • the “adduct” is a mixture of the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a compound having a molecular active hydrogen, and examples thereof include an adduct of xylylene diisocyanate of trimethylolpropane as described later.
  • the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and having an isocyanate group at the terminal of the molecule.
  • organic polyvalent isocyanate compound more specifically, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane To all or some of the hydroxyl groups of polyols such as tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate. Two or more compounds are added; lysine diisocyanate.
  • organic polyvalent imine compound examples include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetramethylolmethane- Tri- ⁇ -aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.
  • a crosslinked structure can be easily introduced into the energy ray-curable resin layer (I) by a reaction with the polymer (b).
  • the content of the crosslinking agent (e) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is based on 100 parts by mass of the total of the energy ray-curable component (a) and the polymer (b).
  • the amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass.
  • thermosetting component (f) examples include an epoxy thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, and a silicone resin. Of these, the epoxy thermosetting resin is preferable.
  • the thermosetting component (f) may be used alone or in combination of two or more.
  • the epoxy-based thermosetting resin contains an epoxy resin (f1), and may further contain a thermosetting agent (f2).
  • Examples of the epoxy resin (f1) include known epoxy resins, and examples thereof include a polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolak epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin. Bifunctional or higher functional epoxy compounds such as resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.
  • the epoxy resin (f1) may be used alone or in combination of two or more.
  • an epoxy resin having an unsaturated hydrocarbon group such as an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, a (meth) acrylamide group or the like is used. Is also good.
  • An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the obtained package is improved.
  • the number average molecular weight of the epoxy resin (f1) is preferably from 300 to 30,000, more preferably from the viewpoint of the curability of the energy ray-curable resin layer (I) and the strength and heat resistance of the cured resin layer (I ′). It is from 400 to 10,000, more preferably from 500 to 3,000.
  • the epoxy equivalent of the epoxy resin (f1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.
  • thermosetting agent (f2) functions as a curing agent for the epoxy resin (f1).
  • examples of the thermosetting agent (f2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule.
  • the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is converted to an anhydride. It is preferably a phenolic hydroxyl group or an amino group.
  • the thermosetting agent (f2) may be used alone or in combination of two or more.
  • thermosetting agents (f2) examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, biphenol, a novolak phenol resin, a dicyclopentadiene phenol resin, and an aralkyl phenol resin.
  • examples of the amine-based curing agent having an amino group include dicyandiamide.
  • the content of the thermosetting agent (f2) is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the epoxy resin (f1).
  • thermosetting component (f) for example, the total content of the epoxy resin (f1) and the thermosetting agent (f2)
  • the content of the thermosetting component (f) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b). Department.
  • the curing accelerator (g) is a component for adjusting the curing speed of the energy ray-curable resin layer (I).
  • Preferred curing accelerators (g) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, imidazoles such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine, etc.
  • the curing accelerator (g) is used, the content of the curing accelerator (g) is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the thermosetting component (f).
  • the general-purpose additive (z) may be a known one and can be arbitrarily selected according to the purpose, and is not particularly limited. Examples thereof include a filler, a coloring agent, a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. And the like.
  • the general-purpose additive (z) may be used alone or in combination of two or more.
  • the filler examples include an inorganic filler and an organic filler, and by using these, the thermal expansion coefficient of the cured resin layer (I ′) can be adjusted.
  • the energy ray-curable resin layer (I) may or may not contain a filler, but if it contains a filler, its content can more effectively reduce the occurrence of warpage. From the viewpoint of suppression, it is preferably 5 to 87% by mass relative to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , More preferably 7 to 78% by mass.
  • the filler include those made of a heat conductive material.
  • the inorganic filler examples include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc .; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers Single crystal fibers of these inorganic fillers; glass fibers and the like.
  • the average particle size of the filler is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 15 ⁇ m, and still more preferably 0.3 to 10 ⁇ m. When the average particle diameter of the filler is in the above range, a decrease in the transmittance of the energy ray-curable resin layer (I) can be suppressed while maintaining the adhesiveness of the cured resin layer (I ′).
  • the energy ray-curable resin composition may or may not contain a coloring agent, but when the coloring agent is contained, the content is preferably as small as possible, and specifically,
  • the amount is preferably less than 5% by mass, more preferably 0%, based on the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). 0.1 mass%, more preferably less than 0.01 mass%, even more preferably less than 0.001 mass%.
  • the energy ray-curable resin composition is obtained by blending each component for constituting the composition.
  • the order of addition of each component is not particularly limited, and two or more components may be added simultaneously.
  • the solvent may be mixed with any of the components other than the solvent to dilute the components in advance, or any of the components other than the solvent may be diluted in advance.
  • a solvent may be used by mixing with these components.
  • the method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; What is necessary is just to select suitably.
  • the temperature and time during addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.
  • the solvent examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; esters such as ethyl acetate; And amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
  • hydrocarbons such as toluene and xylene
  • alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol
  • esters such as ethyl acetate
  • amides compounds having an amide bond
  • dimethylformamide and N-methylpyrrolidone Among these, methyl ethyl ketone, toluene, and ethyl acetate are preferable in that the components contained in the energy ray-curable resin composition can be more uniformly
  • the energy ray-curable resin layer (I) may have a single-layer configuration or a configuration including two or more layers.
  • Examples of the energy ray-curable resin layer (I) composed of two or more layers include, for example, an energy ray-curable resin layer (I-) for providing a cured resin layer (I ′) having a high storage elastic modulus E ′. i) and an energy ray-curable resin layer (I-ii) having a high adhesive strength.
  • the object to be sealed can be firmly fixed and After the curing, the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (Ii) effectively suppresses the warpage. Performance can be more highly compatible.
  • the preferred composition and physical properties of the energy ray-curable resin layers (Ii) and (I-ii) depend on the desired function from the above-described preferred composition and physical properties of the energy ray-curable resin layer (I). What is necessary is just to select suitably and apply.
  • the thickness of the energy ray-curable resin layer (I) is preferably 1 to 500 ⁇ m, more preferably 5 to 300 ⁇ m, further preferably 10 to 200 ⁇ m, still more preferably 15 to 100 ⁇ m, and still more preferably 20 to 50 ⁇ m. is there.
  • the thickness of the energy ray-curable resin layer (I) is equal to or more than the lower limit, a cured sealing body in which warpage is more effectively suppressed can be obtained. , And excellent curability can be obtained.
  • the “thickness of the energy-ray-curable resin layer (I)” means the entire thickness of the energy-ray-curable resin layer (I), for example, two or more energy-ray-curable resin layers.
  • the thickness of (I) means the total thickness of all the layers constituting the energy ray-curable resin layer (I).
  • the storage elastic modulus E ′ of the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) is such that the curl is suppressed and warpage is suppressed with the cured resin layer having a flat surface.
  • it is 1.0 ⁇ 10 7 Pa or more, more preferably 1.0 ⁇ 10 8 Pa or more, still more preferably 5.0 ⁇ 10 8 Pa or more, and still more.
  • It is preferably 1.0 ⁇ 10 9 or more, more preferably 1.0 ⁇ 10 13 Pa or less, more preferably 1.0 ⁇ 10 12 Pa or less, further more preferably 5.0 ⁇ 10 11 Pa or less. More preferably, it is 1.0 ⁇ 10 11 Pa or less.
  • the visible light (wavelength: 380 nm to 750 nm) transmittance of the energy ray-curable resin layer (I) is preferably 5% or more, more preferably 10% or more, further preferably 30% or more, and still more preferably 50% or more. It is. When the visible light transmittance is in the above range, sufficient energy ray curability can be obtained.
  • the upper limit of the visible light transmittance is not limited, but may be, for example, 95% or less.
  • the transmittance can be measured according to a known method using a spectrophotometer.
  • the pressure-sensitive adhesive layer (X), the base material (Y), and the energy ray-curable resin layer (I) are separately formed so that these have a desired configuration. It can be manufactured by laminating. Each layer can be formed, for example, by applying and drying a resin composition for forming each layer on a release material.
  • the manufacturing method of the laminate of one embodiment of the present invention is not limited to the above method.
  • the base material (Y) is formed on the pressure-sensitive adhesive layer (X) formed on the release material.
  • a method for manufacturing a cured sealing body according to one embodiment of the present invention is a method for manufacturing a cured sealing body using the laminate according to one embodiment of the present invention, and includes the following steps (i) to (iv). Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate. Step (ii): Applying the energy ray-curable resin layer (I).
  • Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by the treatment for expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer.
  • the cured sealing body in one embodiment of the present invention is obtained by covering an object to be sealed with a sealing material and curing the sealing material. There, composed of a cured product of the sealing object and the sealing material.
  • FIG. 4 is a schematic cross-sectional view showing a step of manufacturing a cured sealing body using the laminate 1a shown in FIG.
  • the respective steps described above will be described with reference to FIG.
  • Step (i) is a step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) included in the laminate of one embodiment of the present invention.
  • the adhesive surface of the adhesive layer (X) of the support layer (II) is attached to the support 50 using the laminate 1a, and the energy ray-curable resin layer ( A state in which the sealing target 60 is placed on a part of the surface of (I) is shown.
  • FIG. 4A illustrates an example in which the stacked body 1a illustrated in FIG. 1A is used; Then, a support, a laminate, and an object to be sealed are laminated or placed in this order.
  • the temperature condition in the step (i) is preferably performed at a temperature at which the thermally expandable particles do not expand, for example, in an environment of 0 to 80 ° C (provided that the expansion start temperature (t) is 60 to 80 ° C). In this case, it is preferable that the heat treatment be performed under an environment lower than the expansion start temperature (t).
  • the support is preferably attached to the entire surface of the adhesive surface of the adhesive layer (X) of the laminate. Therefore, the support is preferably plate-shaped. Further, as shown in FIG. 4, the area of the surface of the support on the side to be adhered to the adhesive surface of the adhesive layer (X) is preferably equal to or larger than the area of the adhesive surface of the adhesive layer (X).
  • the material constituting the support is appropriately determined in consideration of the required properties such as mechanical strength and heat resistance according to the type of the object to be sealed, the type of the sealing material used in step (ii), and the like. Selected. Specific examples of the material constituting the support include: metal materials such as SUS; nonmetallic inorganic materials such as glass and silicon wafer; epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic, polyimide resin, Resin materials such as polyamideimide resin; composite materials such as glass epoxy resin; and the like, among which SUS, glass, and silicon wafer are preferable.
  • the support is preferably made of a transparent material such as glass from the viewpoint that the energy ray-curable resin layer (I) can be irradiated with energy rays through the support.
  • the engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like.
  • Examples of the super engineering plastic include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).
  • the thickness of the support is appropriately selected according to the type of the object to be sealed, the type of the sealing material used in step (ii), and the like, but is preferably 20 ⁇ m or more and 50 mm or less, more preferably 60 ⁇ m or more. It is 20 mm or less.
  • a sealing target placed on a part of the surface of the energy ray-curable resin layer (I) for example, a semiconductor chip, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, And a substrate for a panel.
  • a semiconductor chip with a cured resin layer can be manufactured by using the laminate of one embodiment of the present invention.
  • a conventionally known semiconductor chip can be used, and an integrated circuit including a circuit element such as a transistor, a resistor, and a capacitor is formed on a circuit surface thereof.
  • the semiconductor chip is preferably mounted so that the back surface opposite to the circuit surface is covered with the surface of the energy ray-curable resin layer (I). In this case, after mounting, the circuit surface of the semiconductor chip is exposed.
  • a known device such as a flip chip bonder or a die bonder can be used.
  • the layout and the number of semiconductor chips to be arranged may be determined as appropriate according to the form of the target package, the number of products to be produced, and the like.
  • the laminated body of one embodiment of the present invention covers a semiconductor chip with a region larger than the chip size with a sealing material, such as FOWLP, FOPLP, or the like. It is preferable that the present invention is applied to a package in which a redistribution layer is formed even in the surface region of FIG. Therefore, the semiconductor chip is mounted on a part of the surface of the energy ray-curable resin layer (I), and a plurality of semiconductor chips are arranged on the surface in a state where they are arranged at regular intervals.
  • a sealing material such as FOWLP, FOPLP, or the like.
  • the semiconductor chips are mounted, and it is more preferable that the plurality of semiconductor chips are mounted on the surface in a state of being arranged in a matrix of a plurality of rows and a plurality of columns at a predetermined interval.
  • the distance between the semiconductor chips may be determined as appropriate depending on the desired package configuration and the like.
  • Step (ii) is a step of irradiating the energy ray-curable resin layer (I) with energy rays to form a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I). is there.
  • FIG. 4B shows a state where the energy ray-curable resin layer (I) is cured in this step to form a cured resin layer (I ′).
  • the kind and irradiation condition of the energy ray are not particularly limited as long as the kind and condition are such that the energy ray-curable resin layer (I) is sufficiently cured to exhibit its function. What is necessary is just to select suitably according to the process which performs.
  • the illuminance of the energy beam during curing of the energy ray-curable resin layer (I) is preferably from 4 to 280 mW / cm 2 , and the amount of energy beam during the curing is preferably from 5 to 1000 mJ / cm 2. It is more preferably 100 to 500 mJ / cm 2 .
  • the type of the energy beam and the irradiation device are as described above.
  • the energy ray may be irradiated from any direction as long as the energy ray can be irradiated to the energy ray-curable resin layer (I).
  • the support (II) and the support 50 may have a light transmittance
  • the light enters through the support (II) and the support 50 (that is, from the surface of the support 50 in FIG. 4B from the side opposite to the adhesive layer (X),
  • the energy ray can be irradiated to the energy ray-curable resin layer (I) and the support 50, the pressure-sensitive adhesive layer (X) and the base material (Y).
  • Step (iii)> the object to be sealed and the surface of the cured resin layer (I ′) at least at the peripheral portion of the object to be sealed are covered with a thermosetting sealing material (hereinafter referred to as “coating treatment”).
  • This is a step of thermally curing the sealing material to form a cured sealing body including the object to be sealed.
  • the covering process first, the object to be sealed and at least the peripheral portion of the object to be sealed on the surface of the cured resin layer (I ′) are covered with a sealing material.
  • the sealing material covers the entire exposed surface of the object to be sealed and also fills the gap between the plurality of semiconductor chips.
  • FIG. 4C shows a state in which the surface of the object 60 to be sealed and the surface of the cured resin layer (I ′) are entirely covered with the sealing material 70.
  • the sealing material has a function of protecting an object to be sealed and elements attached thereto from an external environment.
  • the sealing material used in the manufacturing method of one embodiment of the present invention is a thermosetting sealing material containing a thermosetting resin. Further, the sealing material may be solid at room temperature, such as granules, pellets, and films, or may be a liquid in the form of a composition. Is preferred.
  • the coating method it is possible to appropriately select and apply the coating method according to the type of the sealing material from the methods applied to the conventional sealing step.
  • a roll lamination method, a vacuum press method, a vacuum lamination method Method, spin coating method, die coating method, transfer molding method, compression molding method and the like can be applied.
  • the sealing material is thermally cured to obtain a cured sealing body in which the object to be sealed is sealed with the sealing material.
  • the thermosetting treatment in the step (iii) is performed at a temperature at which the thermally expandable particles do not expand. It is preferable that the heat treatment be performed under a temperature condition lower than the temperature (t).
  • the cured resin layer (I ′) is provided on the surface on the sealing object 60 side sealed with the sealing material 70.
  • a thermosetting treatment is performed. Since the cured resin layer (I ′) is provided, the difference in shrinkage stress between the two surfaces of the obtained cured sealing body can be reduced, and the warpage generated in the cured sealing body can be effectively suppressed. Conceivable.
  • FIG. 4D shows a state where the heat-expandable particles are separated at the interface P between the cured resin layer (I ′) and the support layer (II) by a process of expanding the particles.
  • a cured resin layer (I ′) having a cured sealing body 80 in which the sealing target 60 is sealed and a cured resin layer (I ′) is provided.
  • the cured sealing body 100 can be obtained.
  • the presence of the cured resin layer (I ') has a function of effectively suppressing the warpage generated in the cured sealing body, protects the sealing object, and improves the reliability of the sealing object. Contribute.
  • the “expansion treatment” in the step (iv) is a treatment for expanding the heat-expandable particles by heating at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles, and the cured resin layer (I Unevenness occurs on the surface of the support layer (II) on the ') side. As a result, it is possible to easily separate the interface P at once with a small force.
  • the “temperature not lower than the expansion start temperature (t)” when expanding the thermally expandable particles is preferably “expansion start temperature (t) + 10 ° C.” or more and “expansion start temperature (t) + 60 ° C.” or less.
  • the temperature is not less than “expansion start temperature (t) + 15 ° C.” and not more than “expansion start temperature (t) + 40 ° C.”.
  • the heating method is not particularly limited, and examples thereof include a heating method using a hot plate, an oven, a baking furnace, an infrared lamp, a hot air blower, and the like. From the viewpoint of facilitating separation at the interface P, a method in which a heat source during heating can be provided on the support 50 side is preferable.
  • the cured sealing body with the cured resin layer thus obtained is further subjected to necessary processing thereafter.
  • One example is described below. In the following description, an embodiment in which the semiconductor chip 60 is used as the sealing target 60 will be described.
  • FIG. 5A shows the cured resin body 100 with the cured resin layer obtained by the above-described manufacturing method
  • FIG. A first grinding step is shown in which the surface 100a on the opposite side is ground by the grinding means 110 to expose the circuit surface 60a of the semiconductor chip 60.
  • the grinding means 110 is not particularly limited, and may be performed using a known grinding device such as a grinder.
  • the surface of the cured sealing body on the cured resin layer (I ′) side is preferably fixed on another support from the viewpoint of workability. Further, from the viewpoint of workability, dicing may be performed to a predetermined size including one or a plurality of chips before the first grinding step.
  • FIG. 5C illustrates a process of forming a rewiring layer 200 and an external terminal electrode 300 that are electrically connected to the circuit surface 60 a of the semiconductor chip 60 exposed on the surface of the cured sealing body 80 by the first grinding process.
  • a wiring layer and an external terminal electrode forming step are shown.
  • the material of the redistribution layer 200 is not limited as long as it is a conductive material, and examples thereof include metals such as gold, silver, copper, and aluminum, and alloys containing these metals.
  • the redistribution layer 200 can be formed by a known method such as a subtractive method or a semi-additive method. If necessary, one or more insulating layers may be provided.
  • the external terminal electrode 300 is electrically connected to an external electrode pad of the redistribution layer 200.
  • the external electronic electrode 300 can be formed, for example, by soldering a solder ball or the like.
  • FIG. 5D shows a step of dicing the cured sealing body 100 with the cured resin layer to which the external terminal electrodes 300 are connected. Dicing may be performed for each semiconductor chip, or may be performed for a predetermined size including a plurality of semiconductor chips.
  • the method for dicing the cured sealing body 100 with the cured resin layer is not particularly limited, and can be implemented by a cutting means such as a dicing saw.
  • FIG. 5E shows a second grinding step of grinding the cured resin layer (I ′) disposed on the side of the cured sealing body 80 opposite to the rewiring layer 200 by the grinding means 110. ing. At this time, the surface of the cured sealing body 80 on the rewiring layer 200 side is preferably fixed with a back grinding tape or the like.
  • the grinding means 110 includes the same means as in the first grinding step. In the second grinding step, a part of the cured resin layer (I ′) may be ground, or the entire cured resin layer (I ′) may be ground. By grinding the cured resin layer (I ′), the size of the obtained semiconductor package can be further reduced.
  • the cured resin layer (I ′) when the second grinding step is not performed or when only a part of the cured resin layer (I ′) is ground, the cured resin layer (I ′) also serves to protect the back surface of the semiconductor chip 60. be able to.
  • the curable resin layer (I) means both the “energy beam curable resin layer (I)” and the “thermosetting resin layer”.
  • the physical property values in each example are values measured by the following methods.
  • ⁇ Measurement of thickness of each layer> The thickness was measured using a constant pressure thickness measuring instrument (model number: “PG-02J”, standard: JIS K6783, Z 1702, Z 1709) manufactured by Teclock Corporation.
  • the expansion start temperature (t) of the thermally expandable particles used in each example was measured by the following method.
  • an aluminum cup having a diameter of 6.0 mm (5.65 mm inner diameter) and a depth of 4.8 mm 0.5 mg of the thermally expandable particles to be measured are added, and an aluminum lid (5.6 mm in diameter, thickness of 0. 1 mm) is prepared.
  • the height of the sample is measured from the upper part of the aluminum lid while a force of 0.01 N is applied to the sample by a pressurizer. Then, with the force of 0.01 N applied by the pressurizer, the heater is heated from 20 ° C.
  • the displacement start temperature be the expansion start temperature (t).
  • the maximum expansion temperature was defined as the temperature at which the amount of displacement measured by the above method became maximum.
  • the curable resin layer (I) of the sheet for forming the curable resin layer (I) produced in each example was attached to a silicon wafer (size: 12 inches, thickness: 100 ⁇ m).
  • a thermosetting resin composition a resin composition obtained by mixing an epoxy resin (manufactured by Struers, product name “Epofix resin”) and a curing agent (manufactured by Struers, product name “Epofix hardener”) A product was prepared, and the resin composition was applied to the surface of the silicon wafer on the side opposite to the curable resin layer (I) so as to have a thickness of 30 ⁇ m.
  • the curable resin layer (I) is the energy ray-curable resin layer (I)
  • the ultraviolet rays are irradiated with an irradiance of 215 mW / cm 2 using an ultraviolet irradiation apparatus RAD-2000 (manufactured by Lintec Corporation). Irradiation was performed three times under the condition of a light amount of 187 mJ / cm 2 to cure the energy ray-curable resin layer (I) to form a cured resin layer (I ′).
  • the curable resin layer (I) was a thermosetting resin layer (I)
  • it was cured by heating at 180 ° C. for 60 minutes to form a cured resin layer (I ′).
  • the thermosetting resin composition is heated and cured to form a thermosetting resin layer, and a cured measurement sample having a cured resin layer (I ′) / silicon wafer / thermosetting resin layer in this order is prepared. Obtained.
  • the “silicon wafer / thermosetting resin layer” portion in the measurement sample after curing has a configuration corresponding to a cured sealing body obtained by sealing a semiconductor chip with a thermosetting resin.
  • the performance of the layer (I ′) as a warp prevention layer can be evaluated.
  • the silicon wafer / thermosetting resin layer was formed in the same procedure as above without attaching the curable resin layer (I)
  • the amount of warpage was 15 mm.
  • the curable resin layer (I) is cured by energy rays or heat to form a cured resin layer (I ').
  • the expandable base material layer (Y1) is expanded by a heat expansion treatment to separate the cured resin layer (I ′) and the support layer (II), and the separation property is evaluated based on the following criteria. did.
  • the curing conditions for the curable resin layer (I) and the thermal expansion treatment for the support layer (II) manufactured in each example were the same as those described in Examples 1 to 5 and Reference Example 1 described later. .
  • A Separable, the appearance of the cured resin layer (I ') is good, and there is no adhesive residue.
  • B Separable, the appearance of the cured resin layer (I ') is good, but adhesive residue is partially present.
  • C It cannot be separated, or there is adhesive residue on the entire surface of the cured resin layer (I ′), or the appearance of the cured resin layer (I ′) is poor.
  • ⁇ Storage modulus E ′ of intumescent base material layer (Y1)> A 200 ⁇ m thick expandable base material layer (Y1) prepared for the measurement of the storage elastic modulus E ′ was 5 mm long ⁇ 30 mm wide ⁇ 200 ⁇ m thick, and a test sample was obtained by removing the release material. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments Co., Ltd., product name “DMAQ800”), the test start temperature is 0 ° C., the test end temperature is 300 ° C., the heating rate is 3 ° C./min, the frequency is 1 Hz, and the amplitude is 20 ⁇ m. The storage elastic modulus E ′ of the test sample at a predetermined temperature was measured under the following conditions.
  • a viscoelasticity measuring device manufactured by Anton Paar, device name "MCR300”
  • a torsional shear method under the conditions of a test start temperature of 0 ° C, a test end temperature of 300 ° C, a heating rate of 3 ° C / min, and a frequency of 1 Hz.
  • ⁇ Storage elastic modulus E ′ of cured resin layer (I ′)> Using a cured specimen of the curable resin layer (I) obtained in each example as a test piece, using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name “DMAQ800”), the test start temperature The storage elastic modulus E ′ of the formed cured resin layer (I ′) was measured at 23 ° C. under the conditions of 0 ° C., a test termination temperature of 300 ° C., a temperature rising rate of 3 ° C./min, a vibration frequency of 11 Hz, and an amplitude of 20 ⁇ m.
  • the test piece was irradiated with ultraviolet light by using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Corporation) at an illuminance of 215 mW. / Cm 2 and a light amount of 187 mJ / cm 2 , and cured by heating three times. If the curable resin layer (I) is a thermosetting resin layer (I), heat at 180 ° C. for 60 minutes. And cured.
  • Synthesis Example 1 (Synthesis of "acrylic urethane resin" used for intumescent base material layer (Y1))
  • isophorone diisocyanate was added to 100 parts by mass of a polycarbonate diol (carbonate type diol) having a mass average molecular weight of 1,000, and the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of isophorone diisocyanate was 1 / L, further added 160 parts by mass of toluene, and reacted at 80 ° C for 6 hours or more with stirring under a nitrogen atmosphere until the isocyanate group concentration reached the theoretical amount.
  • a polycarbonate diol carbonate type diol having a mass average molecular weight of 1,000
  • Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) 80.0 / 20.0 (mass ratio) An acrylic copolymer having a Mw of 600,000.
  • Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid 86.0 / 8.0 / 5.0 / 1.
  • ⁇ Release material> -Heavy release film manufactured by Lintec Co., Ltd., product name "SP-PET382150", a polyethylene terephthalate (PET) film provided with a release agent layer formed of a silicone release agent on one surface, thickness: 38 ⁇ m.
  • -Light release film manufactured by Lintec Co., Ltd., product name "SP-PET381031”
  • a PET film provided with a release agent layer formed of a silicone release agent on one side of the PET film, thickness: 38 ⁇ m.
  • (1-1) Formation of First Pressure-Sensitive Adhesive Layer (X1) 5.0 parts by mass of the isocyanate-based crosslinking agent (i) was added to 100 parts by mass of the solid content of the acrylic copolymer (i) as an adhesive resin. Parts were mixed, diluted with toluene, and uniformly stirred to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass. Then, the pressure-sensitive adhesive composition is applied to a surface of the release agent layer of the heavy release film (hereinafter, also referred to as a “release treated surface”) to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds.
  • a surface of the release agent layer of the heavy release film hereinafter, also referred to as a “release treated surface”
  • a first pressure-sensitive adhesive layer (X1) which was a non-thermally-expandable pressure-sensitive adhesive layer having a thickness of 5 ⁇ m, was formed.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1) at 23 ° C. was 2.5 ⁇ 10 5 Pa.
  • the adhesion at 23 ° C. of the first pressure-sensitive adhesive layer (X1) measured based on the above method was 0.3 N / 25 mm.
  • Second pressure-sensitive adhesive layer (X2) 0.8 mass of the isocyanate-based crosslinking agent (i) is added to 100 mass parts of the solid content of the acrylic copolymer (ii), which is a pressure-sensitive resin. Parts were mixed, diluted with toluene, and uniformly stirred to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass. Then, the pressure-sensitive adhesive composition is applied to the release-treated surface of the light release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to form a second pressure-sensitive adhesive layer having a thickness of 10 ⁇ m ( X2).
  • the storage shear modulus G ′ (23) of the second pressure-sensitive adhesive layer (X2) was 9.0 ⁇ 10 4 Pa. Further, the adhesion at 23 ° C. of the second pressure-sensitive adhesive layer (X2) measured according to the above method was 1.0 N / 25 mm.
  • a 50 ⁇ m thick polyethylene terephthalate (PET) film manufactured by Toyobo Co., Ltd., product name “Cosmoshine A4100”, probe tack value: 0 mN / 5 mm ⁇
  • the resin composition was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to form an intumescent base material layer (Y1) having a thickness of 50 ⁇ m.
  • the PET film as the non-expandable base material corresponds to the non-expandable base material layer (Y2).
  • the base material (Y) including the 50 ⁇ m-thick expandable base material layer (Y1) and the 50 ⁇ m-thick non-expandable base material layer (Y2) was produced.
  • the resin composition was applied to the release-treated surface of the light release film to form a coating film, The coating film was dried at an ambient temperature of 100 ° C. for 120 seconds to form a 200 ⁇ m thick expandable base material layer (Y1) in the same manner. Then, based on the above-described measurement method, the storage elastic modulus and the probe tack value at each temperature of the expandable base material layer (Y1) were measured.
  • the measurement results were as follows.
  • Production Example 2 (Supporting layer (II-B))
  • the heat-expandable particles A were changed to the following heat-expandable particles B, and the drying conditions after applying the resin composition to form a coating film were changed to an atmosphere temperature of 100 ° C. for 1 minute. Except for this, in the same manner as in Production Example 1, a sheet for forming a support layer (II-B) was produced.
  • Production Example 3 (Support layer (II-C))
  • the heat-expandable particles A were changed to the following heat-expandable particles C, and the drying conditions after applying the resin composition to form a coating film were changed to an atmosphere temperature of 100 ° C. for 1 minute. Except for this, in the same manner as in Production Example 1, a sheet for forming a support layer (II-C) was produced.
  • the drying temperature after applying the resin composition to form a coating film is set to the expansion starting temperature of the thermally expandable particles (although it was higher than t), no foaming was observed in the formed support layer (II) because the drying temperature was the ambient temperature.
  • Production Example 4 (Support layer (II-D))
  • the heat-expandable particles A were changed to the following heat-expandable particles D, and the drying conditions after applying the resin composition to form a coating film were changed to an atmosphere temperature of 100 ° C. for 1 minute. Except for this, in the same manner as in Production Example 1, a sheet for forming a support layer (II-D) was produced.
  • the solution of the curable composition prepared above was applied on the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes, and the energy beam having a thickness of 25 ⁇ m was obtained.
  • the curable resin layer (IA) was formed, and a sheet for forming the energy ray-curable resin layer (IA) composed of the energy ray-curable resin layer (IA) and the light release film was prepared.
  • the solution of the curable composition prepared above was applied on the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes, and the energy beam having a thickness of 25 ⁇ m was obtained.
  • the curable resin layer (IB) was formed, and a sheet for forming the energy ray-curable resin layer (IB) including the energy ray-curable resin layer (IB) and the light release film was prepared.
  • Production Example 7 (Thermosetting resin layer (IC)) The following types and amounts (all of which are “active ingredient ratios”) are blended, diluted with methyl ethyl ketone, and uniformly stirred to obtain a solid concentration (active ingredient concentration) of 61% by mass. A solution of the acidic composition was prepared.
  • Acrylic polymer butyl acrylate (BA) (1 part by mass), methyl acrylate (MA) (74 parts by mass), glycidyl methacrylate (GMA) (15 parts by mass) and 2-hydroxyethyl acrylate ( HEA) (10 parts by mass) acrylic resin (glass transition temperature: 8 ° C., Mw: 440,000): 18 parts by mass liquid bisphenol A type epoxy resin (product name: Nippon Shokubai Co., Ltd.) BPA328 ”): 3 parts by mass, solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name" Epicoat 1055 ”): 20 parts by mass, dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name" XD-1000L ”): 1.5 parts by mass dicyandiamide (ADEKA Corp., product name” Adecover donor 3636AS ”): 0.5 quality Part: imidazole (manufactured by Shikoku Kasei Kog
  • thermosetting resin layer (IC) was formed, and a thermosetting resin layer (IC) forming sheet composed of the thermosetting resin layer (IC) and the light release film was prepared.
  • thermosetting sealing resin film which is a stopper material
  • the sealing resin film is heat-cured using a vacuum heating / pressurizing laminator (product name: 7024HP5, manufactured by ROHM and HAAS) and cured and sealed.
  • a stop body was produced.
  • the sealing conditions are as follows. ⁇ Preheating temperature: 100 ° C for both table and diaphragm ⁇ Evacuation: 60 seconds ⁇ Dynamic press mode: 30 seconds ⁇ Static press mode: 10 seconds ⁇ Sealing temperature: 180 ° C. ⁇ 60 minutes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne un produit stratifié comprenant une couche de résine durcissable par rayonnement d'énergie (I), et une couche de support (II) qui supporte la couche de résine durcissable par rayonnement d'énergie (I), la couche de résine durcissable par rayonnement d'énergie (I) ayant une surface adhésive, la couche de support (II) comprenant un substrat (Y) et une couche adhésive, au moins le substrat (Y) et la couche adhésive contenant des particules thermiquement expansibles, et la couche de support (II) et une couche de résine durcie (I') obtenues par durcissement de la couche de résine durcissable par rayonnement d'énergie (I) étant séparées au niveau de la limite entre elles, par un procédé d'expansion des particules thermiquement expansibles.
PCT/JP2018/036812 2018-10-02 2018-10-02 Produit stratifié et procédé de production d'un corps d'étanchéité durci WO2020070790A1 (fr)

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