WO2019187249A1 - Corps multicouche pouvant empêcher le gauchissement d'un corps étanche durci et procédé de production d'un corps étanche durci - Google Patents

Corps multicouche pouvant empêcher le gauchissement d'un corps étanche durci et procédé de production d'un corps étanche durci Download PDF

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Publication number
WO2019187249A1
WO2019187249A1 PCT/JP2018/036813 JP2018036813W WO2019187249A1 WO 2019187249 A1 WO2019187249 A1 WO 2019187249A1 JP 2018036813 W JP2018036813 W JP 2018036813W WO 2019187249 A1 WO2019187249 A1 WO 2019187249A1
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Prior art keywords
layer
resin layer
curable resin
cured
mass
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PCT/JP2018/036813
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English (en)
Japanese (ja)
Inventor
洋佑 高麗
明徳 佐藤
高志 阿久津
康彦 垣内
岡本　直也
忠知 山田
中山　武人
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リンテック株式会社
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Priority to CN201880091676.2A priority Critical patent/CN111886309B/zh
Priority to KR1020207015352A priority patent/KR102576310B1/ko
Priority to JP2020509575A priority patent/JP7240378B2/ja
Publication of WO2019187249A1 publication Critical patent/WO2019187249A1/fr

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    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • 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
    • C09J7/35—Heat-activated
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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 laminate for warping prevention of a cured encapsulant and a method for producing the cured encapsulant.
  • CSP Chip Scale Package
  • WLP Wafer Level Package
  • PLP Panel Level Package
  • WLP and PLP are classified into fan-in type and fan-out type.
  • fan-out type WLP hereinafter also referred to as “FOWLP”
  • PLP hereinafter also referred to as “FOPPL”
  • a sealing material so as to be an area larger than the chip size.
  • the re-wiring layer and the external electrode 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 placement step of placing a plurality of semiconductor chips on a temporary fixing sheet, a covering step of covering with a thermosetting sealing material, and curing the sealing material by thermosetting.
  • Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporarily fixing when cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material.
  • a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material.
  • FOWLP and FOPLP it is also conceivable to use the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1.
  • the thermally expandable particles are heated by heating the temporary fixing layer. It was found that there is a possibility that the temporary cured layer cannot be peeled off from the cured resin layer formed by the first stage heating prior to the heating foaming. This problem tends to become more prominent as the package size increases, such as FOWLP and FOPLP.
  • the cured sealing body in which the peeling failure has occurred may not only damage the sealing target itself such as a semiconductor chip, but also, for example, a part of the thermally expandable adhesive layer may remain on the cured resin layer or be cured. If the resin layer itself is damaged, there may be a negative effect such that the process such as grinding and dicing of the cured sealing body scheduled in the next process cannot be performed accurately.
  • the present invention has a support layer and a curable resin layer, and can perform a sealing process by fixing an object to be sealed to the surface of the curable resin layer.
  • a layer for warpage prevention which can provide a cured resin layer as a warp prevention layer to a cured sealing body formed by processing, and can prevent occurrence of defective peeling between the curable resin layer and the support layer. It is an object of the present invention to provide a method for producing a cured sealing body using a laminate and a warp-preventing laminate.
  • the present inventors have found that the above problems can be solved by setting the adhesive strength of the curable resin layer within a predetermined range, and the present invention has been completed. did. That is, the present invention provides the following [1] to [10].
  • the curable resin layer (I) has an adhesive surface having adhesiveness
  • the support layer (II) has a base material (Y) and an adhesive layer (V), and at least one of the base material (Y) and the adhesive layer (V) includes thermally expandable particles,
  • the curable resin layer (I), the pressure-sensitive adhesive layer (V), and the base material (Y) are arranged in this order, and the pressure-sensitive adhesive surface of the curable resin layer (I) is the pressure-sensitive adhesive layer (V).
  • the minimum curing temperature (T 1 ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I ′) is higher than the foaming start temperature (T 2 ) of the thermally expandable particles.
  • T 2 foaming start temperature
  • the curable resin layer (I) has two or more thermosetting resin layers (X1), and the minimum curing minimum temperature (T 1 ) in the two or more thermosetting resin layers (X1)
  • the substrate (Y) has an expandable substrate layer (Y1) containing the thermally expandable particles.
  • the substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1)
  • the support layer (II) according to the above [5] or [6], wherein the support layer (II) has a non-expandable substrate layer (Y2), an expandable substrate layer (Y1), and an adhesive layer (V) in this order.
  • the curable resin layer (I) has a first layer disposed on the support layer (II) side, and a second layer disposed on the adhesive surface side,
  • the first layer is a thermosetting resin layer (X1-1),
  • a method for producing a cured encapsulant comprising: obtaining a cured encapsulant.
  • a method for producing a cured encapsulant using the warp-preventing laminate according to [8] above Placing a sealing object on a part of the adhesive surface of the curable resin layer (I) of the laminate for warpage prevention; Irradiating energy rays to cure the energy ray curable resin layer (X2); Coating the sealing object and the adhesive surface of the curable resin layer (I) at least in the peripheral part of the sealing object with a thermosetting sealing material; The sealing material is thermally cured to form a cured sealing body including the sealing object, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I ′), A method for producing a cured encapsulant with a cured resin layer, comprising: obtaining a cured encapsulant with a cured resin layer.
  • a sealing object can be fixed to the surface of the curable resin layer to perform a sealing process, and the cured sealing body formed by the sealing process can be used as a warp prevention layer.
  • a laminate for warpage prevention which can be provided with a cured resin layer and can prevent the occurrence of defective peeling between the curable resin layer and the support layer, and a cured seal using the laminate for warpage prevention
  • a method for manufacturing a stationary body can be provided.
  • the target layer is a “non-expandable layer” is determined by performing a treatment for expansion for 3 minutes and then calculating a volume change rate calculated from the following formula before and after the treatment. Is less than 5%, it is determined that the layer is a “non-intumescent 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 for 3 minutes may be performed at the expansion start temperature (t) of the thermally expandable particles.
  • the expansion start temperature (t) may be referred to as the foam start temperature (T2).
  • the “active ingredient” refers to a component excluding a diluent 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, specifically a value measured based on the method described in Examples. It is.
  • GPC gel permeation chromatography
  • (meth) acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit value and the upper limit value described in a stepwise manner can be independently combined for a preferable numerical range (for example, a range such as content). For example, from the description “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.
  • energy beam means an electromagnetic wave or charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, and electron beams.
  • Ultraviolet rays can be irradiated 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 ray source.
  • the electron beam can be emitted by an electron beam accelerator or the like.
  • energy ray curable means a property that cures when irradiated with energy rays
  • non-energy ray curable means a property that does not cure even when irradiated with energy rays. To do.
  • the minimum temperature at which the curing of the curable resin is completed within 2 hours may be referred to as “the minimum curing temperature”.
  • “curing is completed” means that when a sample is measured using a differential scanning calorimeter, a peak attributed to the curing reaction disappears from the temperature characteristic curve.
  • the warpage preventing laminate of one embodiment of the present invention includes a curable resin layer (I) including a thermosetting resin layer (X1) and a support layer (II) that supports the curable resin layer (I). .
  • the warp preventing laminate may be simply referred to as a “laminate”.
  • the thermosetting resin layer (X1) is preferably laminated directly on the support layer (II).
  • the curable resin layer (I) has an adhesive surface having adhesiveness.
  • the support layer (II) has a base material (Y) and a pressure-sensitive adhesive layer (V), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contains thermally expandable particles.
  • the curable resin layer (I), the pressure-sensitive adhesive layer (V), and the base material (Y) are arranged in this order, and the pressure-sensitive adhesive surface of the curable resin layer (I) is the pressure-sensitive adhesive layer (V). It is arranged on the opposite side.
  • the minimum curing temperature (T 1 ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I ′) is higher than the foaming start temperature (T 2 ) of the thermally expandable particles. It is low temperature.
  • FIGS. 1 to 5 are schematic cross-sectional views of the laminates showing the configurations of the warp preventing laminates according to the first to fifth aspects of the present invention.
  • the adhesive surface of the adhesive layer (V1) attached to a support (not shown) and the first surface (support layer) of the curable resin layer (I) From the standpoint of protecting the surface of the curable resin layer (I) and the support layer (II), a release material may be further laminated on the surface opposite to (II). The release material is peeled off and removed when the warp preventing laminate is used.
  • Laminate 1a, 1b is equipped with base material (Y) and support layer (II) which has an adhesive layer (V1), and curable resin layer (I), and base material (Y) and curable resin layer (I) and the direct lamination.
  • first surface the surface of the curable resin layer (I) opposite to the support layer (II)
  • second surface the surface on the support layer (II) side
  • the first surface of the curable resin layer (I) is an adhesive surface having a predetermined adhesive force. When the sealing object is placed, the sealing object can be fixed by the adhesive force.
  • the adhesive surface of an adhesive layer (V1) is affixed on the support body which is not shown in figure.
  • a base material (Y) has an expandable base material layer (Y1) containing a heat-expandable particle.
  • the base material (Y) may be a single-layer base material composed of only the expandable base material layer (Y1) as in the laminate 1a shown in FIG. 1 (a), or FIG. 1 (b).
  • the base material of the multilayer structure which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) may be sufficient.
  • the base material (Y) which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) in the curvature prevention laminated body of a 1st aspect, as shown in FIG.1 (b).
  • the non-intumescent base material layer (Y2) is laminated on the surface of the pressure-sensitive adhesive layer (V1), and the inflatable base material layer (Y1) is laminated on the surface of the non-intumescent base material layer (Y2). It is preferable to have.
  • the heat-expandable particles contained in the expandable base material layer (Y1) are expanded by an expansion process by heating (hereinafter referred to as “heat expansion process”). Unevenness is generated on the surface of (Y), and the contact area with the cured resin layer formed by curing the curable resin layer (I) decreases.
  • a layer obtained by curing a curable resin layer is referred to as a cured resin layer (I ′).
  • the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (V1) is stuck to a support (not shown).
  • the adhesive layer (V1) is affixed so as to be sufficiently adhered to the support, whereby the surface of the expandable substrate layer (Y1) on the pressure-sensitive adhesive layer (V1) side has a force to cause irregularities. Even if this occurs, a force repelling from the pressure-sensitive adhesive layer (V1) is likely to occur. Therefore, it is difficult for irregularities to be formed on the surface of the base material (Y) on the pressure-sensitive adhesive layer (V1) side. As a result, the laminated body 1a can be easily separated at once by a slight force at the interface P between the base material (Y) of the support layer (II) and the cured resin layer (I ′).
  • the interface between the curable resin layer (I) and the support layer (II) may also be referred to as “interface P”.
  • the base material (Y) has an expandable group 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 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 to be transmitted to the pressure-sensitive adhesive layer (V1).
  • the surface of the pressure-sensitive adhesive layer (V1) on the support side is hardly uneven, and the adhesiveness between the pressure-sensitive adhesive layer (V1) and the support is hardly changed before and after the heat expansion treatment and maintains good adhesion. can do.
  • corrugation is easy to be formed in the surface at the side of the curable resin layer (I) of an expandable base material layer (Y1), As a result, the expandable base material layer (Y1) and cured resin layer of a support layer (II) At the interface P with (I ′), the separation can be easily performed with a slight force.
  • an expandable base material layer (Y1) and curable resin layer (I) directly laminate
  • the pressure-sensitive adhesive layer (V1) is preferably laminated on the surface opposite to the adhesive resin layer (I).
  • an adhesive layer or an anchor layer for adhering the two may be provided between the expandable base material layer (Y1) and the non-expandable base material layer (Y2), or may be directly laminated. .
  • the warp preventing laminate of the second aspect of the present invention include warp preventing laminates 2a and 2b shown in FIG.
  • the pressure-sensitive adhesive layer included in the support layer (II) includes the first pressure-sensitive adhesive layer (V1-1) and the second pressure-sensitive adhesive layer (V1-2), and the first pressure-sensitive adhesive layer ( V1-1) and the second pressure-sensitive adhesive layer (V1-2) sandwich the substrate (Y), and the pressure-sensitive adhesive surface of the second pressure-sensitive adhesive layer (V1-2) is bonded to the curable resin layer (I). It has a directly stacked configuration.
  • the pressure-sensitive adhesive layers when the support layer (II) includes a plurality of pressure-sensitive adhesive layers, and the pressure-sensitive adhesive layers when the support layer (II) includes a single pressure-sensitive adhesive layer are collectively referred to. It may be called an adhesive layer (V).
  • the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (V1-1) is attached to a support not shown.
  • the base material (Y) preferably has an expandable base material 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 the laminate 2a shown in FIG. 2 (a).
  • the base material of a multilayer structure which has an expandable base material layer (Y1) and a non-expandable base material layer (Y2) may be sufficient.
  • a base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2).
  • Y1 expandable base material layer
  • Y2 non-expandable base material layer
  • the second pressure-sensitive adhesive layer (V1-2) is laminated on the surface of the expandable base material layer (Y1), and the first pressure-sensitive adhesive layer (V1-1) is formed on the surface of the non-expandable base material layer (Y2). It is preferable to have a laminated structure.
  • the thermally expandable particles in the expandable substrate layer (Y1) constituting the substrate (Y) are expanded by the heat expansion treatment, and the surface of the expandable substrate layer (Y1) is expanded. Unevenness occurs. Then, the second pressure-sensitive adhesive layer (V1-2) is pushed up by the unevenness generated on the surface of the expandable base material layer (Y1), and unevenness is also formed on the pressure-sensitive adhesive surface of the second pressure-sensitive adhesive layer (V1-2). Therefore, the contact area between the second pressure-sensitive adhesive layer (V1-2) and the cured resin layer (I ′) is reduced.
  • the separation can be easily and collectively performed with a slight force at the interface P between the second pressure-sensitive adhesive layer (V1-2) and the cured resin layer (I ′) of the support layer (II).
  • the expandable group of the base material (Y) of the support layer (II) is preferably laminated directly.
  • the laminated body 3 shown in FIG. 3 has the 1st adhesive layer (V1) which is a non-expandable adhesive layer in the one surface side of a base material (Y), and the other side of a base material (Y).
  • V1 1st adhesive layer
  • Y base material
  • Y base material
  • V2 second pressure-sensitive adhesive layer
  • V2 second pressure-sensitive adhesive layer
  • the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (V1) is attached to a support not shown.
  • the base material (Y) which the laminated body 3 of this 3rd aspect has is comprised from the non-expandable base material layer (Y2).
  • the heat-expandable treatment causes the thermally expandable particles in the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer, to expand, and the second pressure-sensitive adhesive layer (V2). Unevenness occurs on the surface, and the contact area between the second pressure-sensitive adhesive layer (V2) and the curable resin layer (I) decreases.
  • the warp preventing laminate 4 of the fourth aspect of the present invention includes the warp preventing laminate 4 shown in FIG.
  • the laminate 4 shown in FIG. 4 has a configuration in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are stacked in this order.
  • the curable resin layer (I) is positioned on the side opposite to the first thermosetting resin layer (X1-1) positioned on the base (Y) side and the base (Y). It consists of a curable resin layer (I) provided with a second thermosetting resin layer (X1-2).
  • thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2) are non-expandable.
  • the second thermosetting resin layer (X1-2) has higher surface adhesive strength than the first thermosetting resin layer (X1-1).
  • those having different characteristics can be used by constituting the curable resin layer (I) with two thermosetting resin layers.
  • a thermosetting resin layer containing a more adhesive composition is selected for the curable resin layer on the side opposite to the support layer (II), and the curable resin layer on the support layer (II) side, Those having better separability from the support layer (II) can be selected.
  • the laminate 5 for warpage prevention shown in FIG. 5 has a configuration in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are stacked in this order.
  • the curable resin layer (I) includes a thermosetting resin layer (X1-1) located on the base (Y) side and an energy ray curing located on the side opposite to the base (Y). It consists of curable resin layer (I) provided with curable resin layer (X2).
  • thermosetting resin layer (X1-1) and the energy beam curable resin layer (X2) are non-expandable.
  • the curable resin layer (I) is divided into an energy ray curable resin layer (X2) and a thermosetting resin layer (X1-1), and those having different characteristics are used. Can do.
  • an energy curable resin layer made of an energy ray curable composition that is easy to adjust so as to have a relatively high adhesive force is disposed, and on the support layer (II) side, A thermosetting resin layer having better separability from a sealing material described later can be disposed.
  • the laminate for warpage prevention of the present embodiment has a sealing object placed on the surface of the curable resin layer, and the sealing object and the thermosetting resin layer at least in the peripheral part of the sealing object.
  • the surface is covered with a sealing material, the sealing material is cured, and the cured sealing body including a sealing object is used for manufacturing a cured sealing body.
  • the specific aspect regarding manufacture of the hardening sealing body using the laminated body for curvature prevention is mentioned later.
  • the sealing object and its surroundings For example, after placing a sealing object on the adhesive surface of an adhesive laminate such as a general wafer mount tape as used in the manufacturing method described in Patent Document 1, the sealing object and its surroundings Consider the case where the adhesive surface of the part is covered with a sealing material, the sealing material is thermally cured, and a cured sealing body is manufactured.
  • the sealing material is thermally cured, the sealing material is subjected to a stress that tends to shrink.
  • the adhesive laminate is fixed to the support, the stress of the sealing material is suppressed.
  • the cured sealing body obtained by separating from the support and the adhesive laminate is difficult to suppress the stress to be contracted.
  • the amount of the sealing material is different between the surface side on the side where the object to be sealed is present and the opposite surface side, and therefore a difference in shrinkage stress is likely to occur.
  • the difference of the shrinkage stress causes the warp generated in the cured sealing body.
  • the cured sealed body after heating is generally separated from the support and the adhesive laminate in a state of being heated to some extent. Therefore, even after the separation, curing of the sealing material proceeds and shrinkage due to natural cooling occurs, so that the cured sealing body is more likely to warp.
  • thermosetting resin layer is also thermoset.
  • the thermosetting resin layer is provided on the surface side on the side where the sealing object which is considered to have a small amount of the sealing material and the shrinkage stress due to the curing of the sealing material is small.
  • the shrinkage stress due to thermosetting of the thermosetting resin layer works. As a result, it is considered that a difference in shrinkage stress between the two surfaces of the cured sealing body can be reduced, and a cured sealing body in which warpage is effectively suppressed can be obtained.
  • thermosetting resin layer which has contributed to suppression of the curvature of a hardening sealing body can be made into a hardening resin layer by thermosetting. That is, by using the laminate for warpage prevention of one embodiment of the present invention, the cured resin layer can be simultaneously formed on one surface of the cured encapsulant by passing through the above-described sealing step. A process for forming the cured resin layer can be omitted, which contributes to an improvement in productivity.
  • At least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contained in the support layer (II) contains thermally expandable particles
  • the minimum curing temperature (T 1 ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I ′) is higher than the foaming start temperature (T 2 ) of the thermally expandable particles. It is low temperature. For this reason, when the said thermally expansible particle is expanded by heating, it can prevent that a peeling defect arises between curable resin layer (I) and support layer (II).
  • At least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contained in the support layer (II) contains thermally expandable particles, and is curable.
  • the minimum curing temperature (T 1 ) at which the curing of the resin layer (I) is completed within 2 hours and becomes the cured resin layer (I ′) is lower than the foaming start temperature (T 2 ) of the thermally expandable particles. is there. For this reason, while the curable resin layer is heated and cured, the thermal expansion of the thermally expandable particles is suppressed.
  • the thermally expandable particles when the thermally expandable particles are thermally expanded, it is avoided that the adhesion between the curable resin layer (I) and the support layer (II) is excessively increased, and a peeling failure occurs between the two. Can be prevented.
  • One reason that the peeling failure is suppressed is not limited to this, but is presumed as follows. While the curable resin layer is heated and cured, when the thermally expandable particles are thermally expanded, irregularities are generated at the interface with the curable resin layer, and the curable resin layer is firmly fixed to the irregularities. For this reason, it is considered that the peelability from the cured resin layer is lowered even if the thermally expandable particles are heated and expanded after the curable resin layer is cured.
  • the thermal expansion of the thermally expandable particles is suppressed while the curable resin layer is heated and cured, so that the thermally expandable particles are thermally expanded after the curing of the curable resin layer is completed.
  • the difference (T 2 ⁇ T 1 ) between the minimum curing temperature (T 1 ) of the curable resin layer (I) and the expansion start temperature (T 2 ) of the thermally expandable particles is preferably 20 to 100 ° C., more preferably Is 20 to 90 ° C, more preferably 20 to 80 ° C.
  • the curable resin layer (I) is a surface on which the sealing object is placed (first surface) from the viewpoint of improving the adhesion with the sealing object. Is preferably sticky.
  • the adhesive strength of the first surface of the curable resin layer (I) is determined by sticking the first surface to a glass plate at a temperature of 70 ° C., the curable property at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min.
  • the resin layer is peeled and measured, preferably 1.7 N / 25 mm or more, more preferably 2.3 N / 25 mm or more, further preferably 3.0 N / 25 mm or more, and further Preferably it is 4.0 N / 25mm or more, Preferably it is 20 N / 25mm or less, More preferably, it is 15 N / 25mm or less, More preferably, it is 10 N / 25mm or less.
  • the first surface of the curable resin layer (I) has an adhesive force of 1.7 N / 25 mm or more, the object to be sealed is fixed when the object to be sealed is fixed to the surface of the curable resin layer (I). This makes it easier to prevent the object from being displaced. If the adhesive force of the 1st surface of curable resin layer (I) is 20 N / 25mm or less, material selection of curable resin layer (I) will become easy.
  • the curable resin layer (I) has an appropriate shearing force from the viewpoint of favorably holding the sealing object when sealing the sealing object. Is preferred. Specifically, a silicon chip (mirror surface) having a thickness of 350 ⁇ m and a size of 3 mm ⁇ 3 mm is used as the above-mentioned measurement adherend and the shear strength for the measurement adherend of the curable resin layer (I) is 70 ° C.
  • the mirror surface of the measurement adherend is pressed and pasted on the curable resin layer and measured at a speed of 200 ⁇ m / s, preferably 20 N / (3 mm ⁇ 3 mm) or more.
  • a speed of 200 ⁇ m / s preferably 20 N / (3 mm ⁇ 3 mm) or more.
  • it is 25 N / (3 mm ⁇ 3 mm), more preferably 30 N / (3 mm ⁇ 3 mm) or more, preferably 100 N / (3 mm ⁇ 3 mm) or less, more preferably 90 N / (3 mm ⁇ 3 mm) or less.
  • the sealing object is fixed to the surface of the curable resin layer (I) and sealed.
  • the shear strength of the curable resin layer (I) with respect to the measurement adherend is 20 N / (3 mm ⁇ 3 mm) or more
  • the sealing object is fixed to the surface of the curable resin layer (I) and sealed.
  • material selection of curable resin layer (I) becomes easy that the said shear strength is 100 N / (3 mm x 3 mm) or less.
  • the adhesive strength of the thermosetting resin layer (X1) is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2. It is ⁇ 8.0 N / 25 mm, more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5 to 4.0 N / 25 mm.
  • the laminate 4 shown in FIG. 4 has the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2), each has the above-mentioned adhesive strength.
  • the adhesive force of the second thermosetting resin layer (X1-2) is preferably higher than the adhesive force of the first thermosetting resin layer (X1-1).
  • the adhesive force of the second thermosetting resin layer (X1-2) is preferably higher than the adhesive force of the first thermosetting resin layer (X1-1).
  • the adhesive strength of the energy ray curable resin layer (X2) alone at room temperature (23 ° C.) is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.8. It is 2 to 8.0 N / 25 mm, more preferably 0.4 to 6.0 N / 25 mm, and still more preferably 0.5 to 4.0 N / 25 mm.
  • the pressure-sensitive adhesive layer (V) (first pressure-sensitive adhesive layer (V1) and second pressure-sensitive adhesive layer (V2)) 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 still more preferably 0.5. -4.0 N / 25 mm.
  • the pressure-sensitive adhesive layer located on the curable resin layer (I) side is opposite to the first pressure-sensitive adhesive layer and the curable resin layer.
  • the pressure-sensitive adhesive layer located in the region may be referred to as a second pressure-sensitive adhesive layer.
  • the first pressure-sensitive adhesive layer (V1-1) ) Or (V1) and the adhesive strength of the second pressure-sensitive adhesive layer (V1-2) or (V2) are preferably in the above ranges, respectively, but the adhesion with the support is improved and the adhesive strength at the interface P is increased.
  • the adhesive force of the first adhesive layer (V1-1) or (V1) to be attached to the support is the second adhesive layer (V1-2) or (V2). It is more preferable that it is higher than the adhesive force of
  • the adhesive force of the 1st surface of curable resin layer (I) is measured in the following procedures. First, the laminated body for warpage prevention provided with the curable resin layer (I) and the support layer (II) is cut into 25 mm width ⁇ 250 mm length (MD direction is 250 mm) to produce a primary sample. Moreover, a glass plate (3 mm float plate glass (JIS R3202 product) manufactured by Yuko Trading Company) is prepared as an adherend.
  • a glass plate (3 mm float plate glass (JIS R3202 product) manufactured by Yuko Trading Company
  • a glass plate is attached so as to be in direct contact with the first surface of the curable resin layer (I) to obtain a test piece.
  • the roller temperature is 70 ° C.
  • the sticking speed is 0.2 m / min.
  • the test piece thus obtained was allowed to stand for 24 hours in an environment of 23 ° C.
  • the shearing force of the curable resin layer (I) is measured by the following procedure. First, a 350 ⁇ m-thick silicon chip having a 3 mm ⁇ 3 mm mirror surface is used as an adherend for measurement. Then, on the first surface of the curable resin layer (I) of each laminate obtained in each Example and Comparative Example described later, the mirror surface of the adherend for measurement is applied at a temperature of 70 ° C. for 1 second at 130 gf. Press and paste. Then, the shear force is measured at a speed of 200 ⁇ m / s using a universal bond tester (DAGE 4000, manufactured by Nordson Advanced Technology).
  • DAGE 4000 manufactured by Nordson Advanced Technology
  • thermosetting resin layer (X1), energy ray curable resin layer (X2) On the surface of the pressure-sensitive adhesive layer (V), thermosetting resin layer (X1) or energy ray-curable resin layer (X2) formed on the release film, a pressure-sensitive adhesive tape (product name “PL Shin” manufactured by Lintec Corporation) is used. ]). Then, the surface of the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy ray curable resin layer (X2) exposed by peeling off the release film is coated with a glass plate (Yuko) as an adherend. It was attached to a float plate glass 3 mm (JIS R3202 product) manufactured by a trading company.
  • the sticking temperature of the pressure-sensitive adhesive layer (V) was 23 ° C.
  • the sticking temperatures of the thermosetting resin layer (X1) and the energy ray curable resin layer (X2) were 70 ° C.
  • 180 degree pulling was performed under the same environment based on JISZ0237: 2000.
  • the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy beam curable resin layer (X2) is peeled off from the glass plate together with the pressure-sensitive adhesive tape at a pulling speed of 300 mm / min.
  • the adhesive strength at 23 ° C. is measured.
  • the support layer (II) and the curable resin are used from the viewpoint of sufficiently fixing the object to be sealed before the curable resin layer (I) is cured and before the expansion treatment so as not to adversely affect the sealing operation.
  • the adhesiveness with the layer (I) is preferably high. From the above viewpoint, in the laminate of one embodiment of the present invention, the interface P between the support layer (II) and the curable resin layer (I) before the curable resin layer (I) is cured and before the thermal expansion treatment is performed.
  • the separation force (F 0 ) at the time of separation 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 or less. is there.
  • the release force (F 0) is a value measured by the following measuring methods. (Measurement of peel force (F 0 )) After the laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), the support layer (II) side of the laminate was placed on a glass plate (float manufactured by Yuko Trading Co., Ltd.) via the adhesive layer.
  • peeling force (F 0 ) The peeling force measured when peeling from ( 1 ) is defined as “peeling force (F 0 )”.
  • the laminate of one embodiment of the present invention includes a support layer (II), a curable resin layer (I), or a cured resin layer (I ′) obtained by curing the curable resin layer (I) by an expansion treatment. At the interface P, separation can be easily performed at a time with a slight force.
  • the curable resin layer (I) is cured to form the cured resin layer (I ′), and then the support layer (II) and the cured resin layer (I) are subjected to an expansion treatment.
  • the peeling force (F 1 ) when separating at the interface P with ') is usually 2,000 mN / 25 mm or less, preferably 1,000 mN / 25 mm or less, more preferably 500 mN / 25 mm or less, more preferably 150 mN / It is 25 mm or less, more preferably 100 mN / 25 mm or less, still more preferably 50 mN / 25 mm or less, and most preferably 0 mN / 25 mm.
  • the release force (F 1) is a value measured by the following measuring methods.
  • the support layer (II) side of the laminate is attached to a glass plate (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Company) via an adhesive layer.
  • a glass plate float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Company
  • the glass plate and the laminate are heated at 130 ° C. for 2 hours to cure the curable resin layer (I) to form the cured resin layer (I ′).
  • the curable resin layer (I) includes the energy ray curable resin layer (X2) as in the laminate 4 in FIG. 4, the energy ray is applied after the thermosetting resin layer (X1-1) is thermally cured.
  • Irradiate energy rays that can cure the curable resin layer (X2) (in the case of ultraviolet rays, irradiate with an illuminance of 215 mW / cm 2 and a light amount of 187 mJ / cm 2 three times) to irradiate the energy ray curable resin layer (X2). Harden.
  • the thermally expandable particles contained in the support layer (II) are expanded. Specifically, the glass plate on which the laminate is affixed is heated at 240 ° C. for 3 minutes, and the thermally expandable particles in the expandable base material layer (Y1) or the expandable pressure-sensitive adhesive layer (V2) of the laminate. Inflates.
  • peeling force (F 1 ) The peeling force measured when peeling at the interface P between the layer (II) and the cured resin layer (I ′) is defined as “peeling force (F 1 )”.
  • the interface P When the cured resin layer (I ′) is completely separated and cannot be fixed for measurement, the measurement is terminated and the peeling force (F 1 ) at that time is set to “0 mN / 25 mm”. .
  • the base material (Y) which support layer (II) has is a non-adhesive base material.
  • the determination as to whether or not the substrate is a non-adhesive substrate has a probe tack value measured in accordance with JIS Z 0237: 1991 of less than 50 mN / 5 mm ⁇ with respect to the surface of the target substrate. Then, the said base material is judged as a "non-adhesive base material". On the other hand, if the probe tack value is 50 mN / 5 mm ⁇ or more, the substrate is determined to be an “adhesive substrate”.
  • the probe tack value on the surface of the substrate (Y) of the support layer (II) used in one embodiment of the present invention is usually less than 50 mN / 5 mm ⁇ , preferably less than 30 mN / 5 mm ⁇ , more preferably less than 10 mN / 5 mm ⁇ . More preferably, it is less than 5 mN / 5 mm ⁇ .
  • the probe tack value on the surface of the substrate (Y) is a value measured by the following measuring method. (Measurement of probe tack value) A substrate to be measured is cut into a square having a side of 10 mm and then left to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity) as a test sample.
  • the probe tack value on the surface of the test sample was measured according to JIS. Measured according to Z0237: 1991. Specifically, a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N / cm 2 for 1 second, and then the probe is moved at a speed of 10 mm / sec. The force required to move away from the surface is measured and the value obtained is taken as the probe tack value for the test sample.
  • the warpage preventing laminate of one embodiment of the present invention has a curable resin layer (I) including a thermosetting resin layer (X1).
  • the curable resin layer (I) is cured to reduce the difference in shrinkage stress between the two surfaces of the cured encapsulant due to the curing of the encapsulant, and the warp that can occur in the resulting cured encapsulant Contributes to the suppression of
  • the curable resin layer (I) becomes a cured resin layer (I ′) by being cured.
  • the cured resin layer (I ′) is formed on one surface of the obtained cured sealing body.
  • the thermal expansion included in the support layer (II) is the lowest curing temperature (T 1 ) at which the curing of the curable resin layer (I) is completed within 2 hours and becomes the cured resin layer (I ′).
  • the temperature is lower than the foaming start temperature (T 2 ) of the conductive particles.
  • T 1 curing temperature
  • T 2 foaming start temperature
  • the storage elastic modulus E ′ at 23 ° C. of the cured resin layer (I ′) is preferably 1. from the viewpoint of obtaining a warp-preventing laminate capable of producing a cured sealing body having a flat surface while suppressing warpage.
  • 0 ⁇ 10 7 Pa or more more preferably 1.0 ⁇ 10 8 Pa or more, further preferably 1.0 ⁇ 10 9 Pa or more, still more preferably 5.0 ⁇ 10 9 Pa or more, and preferably It is 1.0 ⁇ 10 13 Pa or less, more preferably 1.0 ⁇ 10 12 Pa or less, further preferably 5.0 ⁇ 10 11 Pa or less, and still more preferably 1.0 ⁇ 10 11 Pa or less.
  • the storage elastic modulus E ′ of the cured resin layer (I ′) is measured by the following procedure. First, after the curable resin layer (I) was laminated to a thickness of 200 ⁇ m, the curing was substantially completed (when the exothermic peak disappeared at 130 ° C. in the measurement using a differential scanning calorimeter). ) Until cured. In the case of the thermosetting resin layers (X1), (X1-1), and (X1-2), the resin is placed in an oven in an air atmosphere, and the resin is heated at 130 ° C. for 2 hours to give a heat of 200 ⁇ m in thickness. The curable resin layer is thermally cured.
  • the energy ray curable resin layer (X2) and the thermosetting resin layer (X1-1) are included, the energy ray is irradiated (in the case of ultraviolet rays, the illuminance is 215 mW / cm 2 and the light amount is 187 mJ / cm 2 three times. Irradiation) to cure the energy ray curable resin layer (X2), and then thermoset the thermosetting resin layer (X1-1) under the above conditions.
  • a dynamic viscoelasticity measuring apparatus (TA Instruments, 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 11 Hz.
  • the storage elastic modulus E ′ of the formed cured resin layer at 23 ° C. is measured under the condition of an amplitude of 20 ⁇ m.
  • the 1st surface which is the surface on the opposite side to a support layer of curable resin layer (I) has adhesiveness.
  • the adhesive force is applied to the glass plate by attaching the first surface at a temperature of 70 ° C., and peeling off the curable resin layer at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min.
  • the value is preferably 1.7 N / 25 mm or more.
  • “applying at a temperature of 70 ° C.” means that the laminated body is a pressing body such as a pressure roller having a heat generation temperature of 70 ° C.
  • the sealing target By pressing on a glass plate, it means sticking a laminated body on a glass plate.
  • the sealing target is placed on the first surface of the curable resin layer (I)
  • the surface of the curable resin layer (I) has the above-described adhesiveness, so that it is in close contact with the sealing target.
  • the sealing object such as a semiconductor chip
  • the sealing object is tilted or the sealing object is disposed and then sealed against the curable resin layer (I). It is possible to prevent the position of the object to be stopped from deviating from the intended position.
  • the shear strength of the curable resin layer (I) to the measurement adherend is 130 gf at a temperature of 70 ° C. with a silicon chip (mirror surface) having a thickness of 350 ⁇ m and a size of 3 mm ⁇ 3 mm as the measurement adherend. It is a value when the mirror surface of the adherend for measurement is pressed and pasted on the curable resin layer for 1 second and measured at a speed of 200 ⁇ m / s, and is preferably 20 N / (3 mm ⁇ 3 mm) or more.
  • the adhesive force of the first surface of the curable resin layer (I) and the shearing force of the curable resin layer (I) on the measurement adherend are the thermosetting resin composition constituting the curable resin layer (I). Or by adjusting the types and blending ratios of the components of the energy beam curable resin composition. Adhesive force and shear force vary depending on the composition and blending ratio of the resin composition, and shear force also varies depending on the configuration of the entire curable resin layer (I). It becomes easy to make it a high value by using the acrylic polymer mentioned later as a polymer component, using an epoxy resin as a thermosetting component, or using a coupling agent. Moreover, about a shear force, it becomes easy to make it a high value by increasing content of an inorganic filler and a crosslinking agent, for example.
  • the thickness of the curable resin layer (I) is preferably 1 to 500 ⁇ m, more preferably 5 to 300 ⁇ m, still more preferably 10 to 200 ⁇ m, and still more preferably 15 to 100 ⁇ m.
  • thermosetting resin layer (X1) The thermosetting resin layers (X1), (X1-1), and (X1-2) may be formed from a thermosetting resin composition containing the polymer component (A) and the thermosetting component (B). preferable.
  • the thermosetting resin layers (X1), (X1-1), and (X1-2) are sometimes collectively referred to as a thermosetting resin layer (X1).
  • the curable resin composition may further contain one or more selected from a colorant (C), a coupling agent (D), and an inorganic filler (E). It is preferable to contain at least an inorganic filler (E) from the viewpoint of suppressing the warpage and obtaining a warp-preventing laminate capable of producing a cured sealing body having a flat surface.
  • the thermosetting resin layer (X1) itself is cured so that the minimum curing temperature (T 1 ) of the curable resin layer (I) satisfies the relationship described above. Is lower than the foaming start temperature (T 2 ) of the thermally expandable particles contained in the support layer (II), when the curing minimum temperature (T 1 ) that completes the cured resin layer (I ′) within 2 hours It is preferable.
  • the minimum curing temperature (T 1 ) of the thermosetting resin layer (X1) is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, more preferably, relative to the foaming start temperature (T 2 ) of the thermally expandable particles. Low by 30 ° C or more.
  • a curing accelerator may be added, the amount of the curing accelerator or the crosslinking agent may be increased, or a monomer that is more easily cross-linked may be selected.
  • the thickness of the thermosetting resin layer (X1) may be in the same numerical range as the thickness of the curable resin layer (I).
  • the thermosetting resin layer (X1) includes a plurality of layers such as the thermosetting resin layers (X1-1) and (X1-2), the total thickness of these layers is the curable resin. What is necessary is just to make it become the numerical value range similar to the thickness of layer (I).
  • the thickness of the thinnest layer among these layers is preferably 10% or more, more preferably 20% or more, and further preferably 30% or more of the thickness of the thickest layer.
  • the curing start temperature of the thermosetting resin layer (X1) is preferably 80 to 200 ° C, more preferably 90 to 160 ° C, and further preferably 100 to 150 ° C.
  • a layer having a curing start temperature lower than the expansion start temperature of the thermally expandable particles is used as the thermosetting resin layer (X1).
  • the curing start temperature of the thermosetting resin layer (X1) is preferably 5 ° C. or less, more preferably 10 ° C. or less, and further preferably 20 ° C. or less than the expansion start temperature of the thermally expandable particles.
  • the polymer component (A) contained in the thermosetting resin composition means a compound having a mass average molecular weight of 20,000 or more and having at least one repeating unit.
  • the thermosetting resin composition contains the polymer component (A)
  • the thermosetting resin layer to be formed has flexibility and film-forming properties, and the property maintaining property of the laminate is improved. be able to.
  • the mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, more preferably 50,000 to 2,000,000, and even more preferably 100,000 to 1,500,000. More preferably, it is 200,000 to 1,000,000.
  • the content of the component (A) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and still more preferably 10% with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. ⁇ 30% by mass.
  • polymer component (A) examples include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber polymers, and the like. These polymer components (A) may be used alone or in combination of two or more.
  • the acrylic polymer having an epoxy group and the phenoxy resin having an epoxy group have thermosetting properties, but these have a mass average molecular weight of 20,000 or more and at least 1 Any compound having a repeating unit of a seed is included in the concept of the polymer component (A).
  • a polymer component (A) contains an acrylic polymer (A1).
  • the content of the acrylic polymer (A1) in the polymer component (A) is preferably from 60 to the total amount (100% by mass) of the polymer component (A) contained in the thermosetting resin composition.
  • the amount is 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
  • the mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3,000,000, more preferably 10 from the viewpoint of imparting flexibility and film forming property to the thermosetting resin layer to be formed. It is 10,000 to 1,500,000, more preferably 150,000 to 1,200,000, still more preferably 250,000 to 1,000,000.
  • the glass transition temperature (Tg) of the acrylic polymer (A1) is produced using a viewpoint of imparting good adhesiveness to the surface of the thermosetting resin layer to be formed, and a warp preventing laminate. From the viewpoint of improving the reliability of the cured encapsulant with a cured resin layer, it is preferably ⁇ 60 to 50 ° C., more preferably ⁇ 50 to 30 ° C., further preferably ⁇ 40 to 10 ° C., and still more preferably ⁇ 35 to 5 ° C.
  • acrylic polymer (A1) examples include polymers having an alkyl (meth) acrylate as a main component. Specifically, the alkyl (meth) acrylate (a1 ′) having an alkyl group having 1 to 18 carbon atoms.
  • An acrylic polymer containing the structural unit (a1) derived from hereinafter also referred to as “monomer (a1 ′)” is preferred, and the functional group-containing monomer (a2 ′) (hereinafter referred to as “monomer ( An acrylic copolymer containing the structural unit (a2) derived from “a2 ′)” is more preferable.
  • Acrylic polymer (A1) may be used independently and may use 2 or more types together.
  • the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer. Good.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 18, more preferably 1 to 12, more preferably 1 to 12, from the viewpoint of imparting flexibility and film forming property to the thermosetting resin layer to be formed. Preferably, it is 1-8.
  • the alkyl group may be a straight chain alkyl group or a branched chain alkyl group. These monomers (a1 ′) may be used alone or in combination of two or more.
  • the monomer (a1 ′) is an alkyl (meth) having an alkyl group having 1 to 3 carbon atoms.
  • An acrylate is preferably contained, and a methyl (meth) acrylate is more preferably contained.
  • the content of the structural unit (a11) derived from the alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is based on the total structural unit (100% by mass) of the acrylic polymer (A1).
  • the content is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 80% by mass.
  • the monomer (a1 ′) preferably contains an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, and more preferably contains an alkyl (meth) acrylate having an alkyl group having 4 to 6 carbon atoms. More preferably, butyl (meth) acrylate is included.
  • the content of the structural unit (a12) derived from the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms is the acrylic polymer (A1). Is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and still more preferably 10 to 60% by mass with respect to all the structural units (100% by mass).
  • the content of the structural unit (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, and still more preferably 55% with respect to the total structural unit (100% by mass) of the acrylic polymer (A1). It is -90 mass%, More preferably, it is 60-90 mass%.
  • the monomer (a2 ′) is preferably at least one selected from hydroxy group-containing monomers and epoxy group-containing monomers.
  • a monomer (a2 ') may be used independently and may use 2 or more types together.
  • hydroxy group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol. Among these, as the hydroxy group-containing monomer, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.
  • Examples of the epoxy-containing monomer include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate.
  • Epoxy group-containing (meth) acrylates such as glycidyl crotonate and allyl glycidyl ether.
  • an epoxy-containing monomer an epoxy group-containing (meth) acrylate is preferable, and glycidyl (meth) acrylate is more preferable.
  • the content of the structural unit (a2) is preferably 1 to 50% by weight, more preferably 5 to 45% by weight, and still more preferably based on the total structural unit (100% by weight) of the acrylic polymer (A1). It is 10 to 40% by mass, more preferably 10 to 30% by mass.
  • the acrylic polymer (A1) may have a structural unit derived from another monomer other than the structural units (a1) and (a2) as long as the effects of the present invention are not impaired.
  • examples of other monomers include vinyl acetate, styrene, ethylene, ⁇ -olefin and the like.
  • thermosetting component (B) plays a role of thermosetting the formed thermosetting resin layer to form a hard cured resin layer, and is a compound having a mass average molecular weight of less than 20,000.
  • the mass average molecular weight (Mw) of the thermosetting component (B) is preferably 10,000 or less, more preferably 100 to 10,000.
  • an epoxy compound (B1) which is a compound having an epoxy group, from the viewpoint of making a cured sealing body having a flat surface while suppressing warpage, which can be produced.
  • a thermosetting agent (B2) and it is more preferable that a curing accelerator (B3) is further included together with the epoxy compound (B1) and the thermosetting agent (B2).
  • Examples of the epoxy compound (B1) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, and bisphenol A type epoxy resins. And epoxy compounds having a bifunctional or higher functionality in the molecule such as a bisphenol F type epoxy resin and a phenylene skeleton type epoxy resin and having a mass average molecular weight of less than 20,000.
  • An epoxy compound (B1) may be used independently and may use 2 or more types together.
  • the content of the epoxy compound (B1) is a polymer contained in the thermosetting resin composition from the viewpoint of making a laminate for warpage prevention capable of producing a cured sealing body having a flat surface while suppressing warpage.
  • the amount is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, still more preferably 10 to 150 parts by mass, and still more preferably 20 to 120 parts by mass with respect to 100 parts by mass of the component (A).
  • the thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1).
  • the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is preferable.
  • the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, and acid anhydrides.
  • a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable from the viewpoint of producing a pressure-sensitive adhesive laminate with a cured resin layer having a flat surface while suppressing warpage, and phenol.
  • An amino group is more preferable, and an amino group is more preferable.
  • thermosetting agent having a phenol group examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zylock type phenolic resins, and aralkylphenolic resins.
  • phenolic thermosetting agent having a phenol group examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zylock type phenolic resins, and aralkylphenolic resins.
  • amine-based thermosetting agent having an amino group examples include dicyandiamide. These thermosetting agents (B2) may be used independently and may use 2 or more types together.
  • the content of the thermosetting agent (B2) is 100 masses of the epoxy compound (B1) from the viewpoint of producing a pressure-sensitive adhesive laminate with a cured resin layer having a flat surface while suppressing warpage.
  • the amount is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass with respect to parts.
  • the curing accelerator (B3) is a compound having a function of increasing the rate of thermosetting when the thermosetting resin layer to be formed is thermoset.
  • the curing accelerator (B3) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine, etc.
  • the content of the curing accelerator (B3) is such that the epoxy compound (B1) and the thermosetting agent (from the viewpoint of making a cured sealing body having a flat surface while suppressing warpage can be produced.
  • the total amount of B2) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and still more preferably 0.3 to 4 parts by mass with respect to 100 parts by mass.
  • thermosetting resin composition used in one embodiment of the present invention may further contain a colorant (C).
  • a colorant C
  • thermosetting resin layer formed from the thermosetting resin composition containing the colorant (C) is thermoset to obtain a cured resin layer, it is easy to determine whether the cured resin layer is stuck or not in appearance.
  • an effect such as blocking infrared rays generated from surrounding devices and preventing malfunction of a sealing object (semiconductor chip or the like).
  • colorant (C) organic or inorganic pigments and dyes can be used.
  • the dye for example, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used. Moreover, it does not restrict
  • black pigments are preferable from the viewpoint of good shielding properties against electromagnetic waves and infrared rays. Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like. From the viewpoint of improving the reliability of the semiconductor chip, carbon black is preferable.
  • these coloring agents (C) may be used independently and may use 2 or more types together.
  • the content of the colorant (C) is 8% by mass with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. It is preferable that it is less than. If content of a coloring agent (C) is less than 8 mass%, it can be set as the laminated body for the curvature prevention which can confirm the presence or absence of the crack of the surface of a chip
  • the content of the colorant (C) is effective for the thermosetting resin composition.
  • it is 0.01 mass% or more with respect to the whole quantity (100 mass%) of a component, More preferably, it is 0.05 mass% or more, More preferably, it is 0.10 mass% or more, More preferably, it is 0.15 mass% That's it.
  • thermosetting resin composition used in one embodiment of the present invention may further contain a coupling agent (D).
  • the thermosetting resin layer formed from the thermosetting resin composition containing the coupling agent (D) can improve the adhesion with the sealing object when the sealing object is placed.
  • the cured resin layer obtained by thermosetting the thermosetting resin layer can also improve water resistance without impairing heat resistance.
  • the compound which reacts with the functional group which a component (A) or a component (B) has is preferable, and a silane coupling agent is specifically preferable.
  • the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (methacryloxy) Propyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropyltrimethoxysilane, N-6- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptoprop
  • the molecular weight of the coupling agent (D) is preferably 100 to 15,000, more preferably 125 to 10,000, more preferably 150 to 5,000, still more preferably 1,75 to 3,000, and even more. Preferably, it is 200 to 2,000.
  • the content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, based on the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. More preferably, it is 0.10 to 4% by mass, and still more preferably 0.15 to 2% by mass.
  • thermosetting resin composition used in one embodiment of the present invention is an inorganic filler (E) from the viewpoint of a warp-preventing laminate capable of producing a cured sealing body having a flat surface while suppressing warpage.
  • thermosetting resin layer formed from a thermosetting resin composition containing an inorganic filler (E) when the sealing material is thermoset, the shrinkage stress between the two surfaces of the cured encapsulant is reduced.
  • the degree of thermosetting of the thermosetting resin layer can be adjusted so as to reduce the difference. As a result, it is possible to manufacture a cured sealing body having a flat surface while suppressing warpage.
  • thermosetting the thermosetting resin layer to be formed can be adjusted to an appropriate range, and the reliability of the object to be sealed can be improved. Moreover, the moisture absorption rate of the said cured resin layer can also be reduced.
  • Examples of the inorganic filler (E) include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, beads formed by spheroidizing them, single crystal fibers, glass fibers, and the like. Non-thermally expandable particles can be mentioned. These inorganic fillers (E) may be used alone or in combination of two or more. Among these, silica or alumina is preferable from the viewpoint of suppressing the warpage to obtain a warp-preventing laminate capable of producing a cured sealing body having a flat surface.
  • the average particle diameter of the inorganic filler (E) is preferably 0.01 to 50 ⁇ m, more preferably from the viewpoint of improving the gloss value of the cured resin layer formed by thermosetting the thermosetting resin layer to be formed.
  • the thickness is 0.1 to 30 ⁇ m, more preferably 0.3 to 30 ⁇ m, and particularly preferably 0.5 to 10 ⁇ m.
  • the content of the component (E) is the total amount of effective components of the thermosetting resin composition from the viewpoint of a warp-preventing laminate capable of producing a cured sealing body having a flat surface while suppressing warpage ( 100% by mass), preferably 25 to 80% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 65% by mass, and still more preferably 45 to 60% by mass.
  • thermosetting resin composition used in one embodiment of the present invention may further contain other additives other than the above components (A) to (E) as long as the effects of the present invention are not impaired.
  • additives include a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a gettering agent, and a chain transfer agent.
  • the total content of additives other than the components (A) to (E) is preferably 0 to 20% by mass with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. More preferably, it is 0 to 10% by mass, and still more preferably 0 to 5% by mass.
  • the curable resin layer (I) is composed of a single layer of the thermosetting resin layer (X1) as shown in FIGS. 1, 2, and 3, this single thermosetting resin layer (X1) Has the above configuration.
  • the curable resin layer (I) has a first thermosetting resin layer (X1-1) located on the support layer (II) side and the side opposite to the support layer (II) (
  • the minimum value (T 1a ) of the minimum curing temperature (T 1 ) in the thermosetting resin layer (X1) is lower than the foaming start temperature (T 2 ) of the thermally expandable particles contained in the support layer (II).
  • thermosetting resin layer (X1) Preferably there is. Even if the minimum curing temperatures (T 1 ) of the plurality of layers included in the thermosetting resin layer (X1) are different, the curable resin layer showing the minimum value (T 1a ) Since it has the lowest curing temperature (T 1 ) lower than the foaming start temperature (T 2 ), the expansion of the thermally expandable particles is suppressed when the curable resin layer is cured, and excessive adhesion to the curable resin layer is achieved. Is prevented. Among the plurality of layers constituting the thermosetting resin layer (X1), this effect is remarkable when the layer having T 1a is disposed on the most support layer side.
  • the peelability between the cured resin layer (I ′) and the support layer (II) can be hardly impaired.
  • the other layer cures in a state where the expansion of the thermally expandable particles is suppressed. Therefore, when the thermally expandable particles are later expanded, they are separated due to the presence of the other layer after curing. It is presumed that this is because of improving the sex.
  • first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2) may have different adhesive forces, for example.
  • the second thermosetting resin layer (X1-2) located on the first surface side has a higher surface adhesiveness than the first thermosetting resin layer (X1-1).
  • a thermosetting resin layer (X1-2) is preferred.
  • higher adhesive force is generated. For example, it is possible to select what is to be reduced, and to reduce the addition ratio of the inorganic filler.
  • the former may be increased by making the shear force of the first thermosetting resin layer (X1-1) different from the shear force of the second thermosetting resin layer (X1-2).
  • the shear force is made larger than that of the second thermosetting resin layer (X1-2). can do.
  • the curable resin layer (I) may include a thermosetting resin layer (X1-1) and an energy beam curable resin layer (X2).
  • the curable resin layer (I) includes a first layer located on the support layer side and a second layer located on the first surface side, and the first layer is a thermosetting resin layer (X1- 1), and the second layer is preferably an energy ray curable resin layer (X2).
  • the thermosetting resin layer (X1-1) has the above-described configuration.
  • the energy ray curable resin layer (X2) is preferably formed from an energy ray curable pressure sensitive adhesive composition containing an energy ray curable pressure sensitive resin and a photopolymerization initiator.
  • the energy ray curable resin layer (X2) is easier to adjust to increase the adhesive force than the thermosetting resin layer, it is easy to reliably fix the object to be sealed to the first surface.
  • the energy ray curable resin layer using such an energy ray curable pressure-sensitive adhesive layer by irradiating it with energy rays, it is possible to cure the encapsulating material as will be described later. Curing shrinkage of the resin layer can be made difficult to occur, which is advantageous in preventing warpage of the cured sealing body.
  • thermosetting pressure-sensitive adhesive composition when heated at a high temperature, it softens mainly in the initial stage of curing, which may cause chip misalignment, whereas the energy ray-curable pressure-sensitive adhesive composition is In addition, since it is not softened by curing with energy beam irradiation, it is possible to avoid the occurrence of chip misalignment associated with curing.
  • energy rays include ultraviolet rays, electron beams, and radiation, but ultraviolet rays are preferable from the viewpoint of availability of the curable resin composition and ease of handling of the energy ray irradiation apparatus.
  • the energy ray-curable pressure-sensitive adhesive composition includes an energy ray-curable pressure-sensitive adhesive resin in which a polymerizable functional group such as a (meth) acryloyl group or a vinyl group is introduced into the side chain of the pressure-sensitive adhesive resin.
  • the composition may contain a monomer or oligomer having a polymerizable functional group.
  • these compositions contain a photoinitiator further.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned. These photoinitiators may be used independently and may use 2 or more types together.
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0 to 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of the monomer or oligomer having a polymerizable functional group. 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and particularly preferably 0.1 to 3 parts by mass.
  • thermosetting resin layer (X1-1) By increasing the shear force of the thermosetting resin layer (X1-1) to be greater than the shear force of the energy ray curable resin layer (X2), the shear force of the entire curable resin layer (I) is increased. May be.
  • the support layer (II) included in the laminate of one embodiment of the present invention has a base material (Y) and a pressure-sensitive adhesive layer (V), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) is hot. It is preferable that it contains expandable particles.
  • support layer (II) is a layer isolate
  • -1st aspect of support layer (II) Support layer (II) provided with the base material (Y) which has the expansible base material layer (Y1) containing a thermally expansible particle.
  • the substrate (Y) has an expandable substrate layer (Y 1) containing thermally expandable particles. Things.
  • the pressure-sensitive adhesive layer (V) is preferably a non-expandable pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer (V1) is A non-intumescent adhesive layer is preferred.
  • both the first pressure-sensitive adhesive layer (V1-1) and the second pressure-sensitive adhesive layer (V1-2) are non-intumescent. It is preferable that it is an adhesive layer. Since the base material (Y) has the expandable base material layer (Y1) as in the first embodiment of the support layer (II), the pressure-sensitive adhesive layer (V1) does not need to be expandable, and is expandable. It is not constrained by the composition, composition and process for imparting. Thereby, in designing the pressure-sensitive adhesive layer (V1), for example, it is possible to design with priority given to performances other than expansibility, such as performance such as adhesiveness, productivity, economy, and the like. V) The degree of freedom in design can be improved.
  • the thickness of the base material (Y) before the expansion treatment is preferably 10 to 1,000 ⁇ m, more preferably 20 to 700 ⁇ m, still more preferably 25 to 500 ⁇ m, and still more.
  • the thickness is preferably 30 to 300 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (V) before the expansion treatment in the first aspect of the support layer (II) is preferably 1 to 60 ⁇ m, more preferably 2 to 50 ⁇ m, still more preferably 3 to 40 ⁇ m, and even more preferably. Is 5 to 30 ⁇ m.
  • the above-mentioned “thickness of the pressure-sensitive adhesive layer (V)” indicates the respective pressure-sensitive adhesive layers. It means the thickness of the adhesive layer (in FIG. 2, the thickness of each of the first adhesive layer (V1-1) and the second adhesive layer (V1-2)). Moreover, in this specification, the thickness of each layer which comprises a laminated body means the value measured by the method as described in an Example.
  • the thickness ratio [(Y1) / (V)] between the expandable substrate layer (Y1) and the pressure-sensitive adhesive layer (V) before the expansion treatment is as follows: Preferably it is 1,000 or less, More preferably, it is 200 or less, More preferably, it is 60 or less, More preferably, it is 30 or less. If the thickness ratio is 1,000 or less, a laminate that can be easily and collectively separated by a slight force at the interface P between the support layer (II) and the cured resin layer (I ′) by expansion treatment. It can be.
  • the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 5.0 or more.
  • the base material (Y) may be composed only of the expandable base material layer (Y1) as shown in FIG.
  • the curable resin layer (I) has an expandable base layer (Y1) and the pressure-sensitive adhesive layer (V) has a non-expandable base layer (Y2). You may have.
  • the thickness ratio [(Y1) / (Y2)] of the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) before the expansion treatment Is preferably 0.02 to 200, more preferably 0.03 to 150, and still more preferably 0.05 to 100.
  • the thickness of the support layer (II) is preferably 0.02 to 200 ⁇ m, more preferably 0.03 to 150 ⁇ m, still more preferably 0.05 to 100 ⁇ m.
  • the 1st adhesive layer (V1) which is a non-expandable adhesive layer is arrange
  • the second surface of the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, is disposed on the other surface.
  • the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer, and the curable resin layer (I) are in direct contact.
  • the substrate (Y) is preferably a non-intumescent substrate.
  • the non-expandable base material is preferably composed only of the non-expandable base material layer (Y2).
  • the second pressure-sensitive adhesive layer (V2) which is an expandable pressure-sensitive adhesive layer and the first pressure-sensitive adhesive layer (non-expandable pressure-sensitive adhesive layer) before the expansion treatment
  • the thickness ratio [(V2) / (V1)] to V1) is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.
  • the thickness ratio [(V2 ) / (Y)] is preferably 0.05 to 20, more preferably 0.1 to 10, and still more preferably 0.2 to 3.
  • the thickness of the support layer (II) is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, still more preferably 0.2 to 3 ⁇ m.
  • the expandable particles used in one embodiment of the present invention can expand by heating to form irregularities on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (V2), and can reduce the adhesive force with the adherend. If it is a thing, it will not specifically limit.
  • Thermally expandable particles are superior in versatility and handleability compared to energy ray expandable particles that expand upon irradiation with energy rays.
  • the average particle diameter of the thermally expandable particles used in one embodiment of the present invention before expansion at 23 ° C. is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, and still more preferably 10 to 50 ⁇ m.
  • the average particle diameter before expansion of the thermally expandable particles is the volume-median particle diameter (D 50 ), and is a laser diffraction particle size distribution measuring device (for example, product name “Mastersizer 3000” manufactured by Malvern).
  • D 50 volume-median particle diameter
  • the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion means a particle diameter corresponding to 50%.
  • the 90% particle diameter (D 90 ) before expansion at 23 ° C. of the thermally expandable particles used in one embodiment of the present invention is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, still more preferably 25 to 90 ⁇ m, More preferably, it is 30 to 80 ⁇ m.
  • the 90% particle diameter (D 90 ) before expansion of the thermally expandable particles is the expansion measured by using a laser diffraction particle size distribution measuring apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern). In the particle distribution of the previous thermally expandable particles, the particle diameter corresponding to 90% of the cumulative volume frequency calculated from the smaller particle diameter of the thermally expandable particles before expansion is meant.
  • the heat-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. Specifically, it is preferably a thermally expandable particle having 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.
  • the expansion start temperature (t) of a thermally expansible particle means the value measured based on the method as described in an Example.
  • the thermally expandable particles include a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an encapsulated component encapsulated in the outer shell and vaporized when heated to a predetermined temperature.
  • a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an encapsulated component encapsulated 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 vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
  • Examples of the inclusion component contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane.
  • Expansion starting temperature of the thermally expandable particles (t) is adjustable by appropriately selecting the type of encapsulated component is adjusted to be higher than the curing lowest temperature T 1 of the curable resin layer (I).
  • the maximum volume expansion coefficient when heated to a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles used in one embodiment of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, Preferably it is 2.5 to 60 times, and more preferably 3 to 40 times.
  • the expandable substrate 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 a surface by an oxidation method, an unevenness forming method, 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), hot air treatment, ozone, and ultraviolet irradiation treatment.
  • the unevenness method include sand blast method and solvent treatment method. Etc.
  • the expandable base material layer (Y1) preferably satisfies the following requirement (1).
  • 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 the examples.
  • the requirement (1) can be said to be an index indicating the rigidity of the expandable base material layer (Y1) immediately before the thermally expandable particles expand.
  • the expandable base material layer (Y1) satisfying the above requirement (1) becomes sufficiently large by expansion of the thermally expandable particles at the expansion start temperature (t), and the curable resin layer (I) is laminated. Unevenness is likely to be formed on the surface of the support layer (II) on the outer side. As a result, a laminate that can be easily separated with a slight 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 requirement (1) is preferably 9.0 ⁇ 10 6 Pa or less, more preferably 8.0 ⁇ 10. 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) defined by the requirement (1) is preferably 1.0 ⁇ 10 3 from the viewpoint of enabling easy separation with a slight force. Pa or more, more preferably 1.0 ⁇ 10 4 Pa or more, and further preferably 1.0 ⁇ 10 5 Pa or more.
  • the expandable substrate layer (Y1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.
  • the substrate additive include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
  • These base material additives may be used alone or in combination of two or more. When these base material additives are contained, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to about 100 parts by mass of the resin. 10 parts by mass.
  • the content of the heat-expandable particles is preferably from 1 to the total mass (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y). It is 40% by mass, 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 a 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, the adhesive resin is polymerizable in the process of forming the expandable substrate layer (Y1) from the resin composition (y).
  • the resin obtained by polymerization reaction with the compound may be a non-adhesive resin, and the expandable base material layer (Y1) containing the resin may be non-adhesive.
  • the mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1,000 to 1,000,000, more preferably 1,000 to 700,000, and still more preferably 1,000 to 500,000. It is. Further, when the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and 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 mass with respect to the total mass (100 mass%) of the expandable base material layer (Y1) or the total amount of active ingredients (100 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 resins and olefin resins. It is preferable to contain seeds or more.
  • acrylic urethane type resin acrylic urethane type resin (U1) formed by superposing
  • urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
  • the urethane prepolymer (UP) is preferably obtained by further subjecting it to a chain extension reaction using a chain extender.
  • Examples of the polyol used as a raw material for the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester / ether type polyols, and carbonate type polyols. These polyols may be used independently and may use 2 or more types together.
  • the polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol and a carbonate diol.
  • ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarbox
  • alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And 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; and the like.
  • alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol
  • ethylene glycol, propylene glycol And alkylene glycols such as diethylene glycol and dipropylene 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 used as a raw material for the urethane prepolymer (UP) examples include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyvalent isocyanates may be used alone or in combination of two or more. These polyisocyanates may be a trimethylolpropane adduct type modified product, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • the polyisocyanate used in one embodiment of the present invention is preferably diisocyanate, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • 2,6 More preferred is at least one selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.
  • alicyclic diisocyanate examples include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane.
  • IPDI isophorone diisocyanate
  • Examples include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferred.
  • the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends.
  • a urethane prepolymer is preferred.
  • an NCO group at the end of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the (meth) acrylic acid ester is preferably at least one selected from alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably used in combination with alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.
  • the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
  • the carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
  • hydroxyalkyl (meth) acrylate the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce
  • vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate.
  • Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide). These may be used alone or in combination of two or more.
  • the content of the (meth) acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably based on 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 alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the vinyl compound. It is 100% by mass, more preferably 80 to 100% by mass, and still 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 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and still more preferably 35 by mass ratio. / 65 to 55/45.
  • the olefin 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 preferable.
  • 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 and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefinic terpolymers such as-(5-ethylidene-2-norborn
  • the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
  • an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride.
  • 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, itaconic anhydride.
  • Glutaconic anhydride citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
  • unsaturated carboxylic acid or its anhydride may be used independently, and may use 2 or more types together.
  • an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin as a main chain.
  • a polymer is mentioned.
  • the number of carbon atoms of the alkyl group contained in the alkyl (meth) acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12.
  • the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
  • Examples of the hydroxyl group-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; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • the resin composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
  • Such 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; acrylonitrile-butadiene-styrene copolymer Polycarbonate; Polyurethane not applicable to acrylic urethane resin; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorine resin etc. are mentioned.
  • vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
  • polystyrene acrylonitrile-butadiene-styren
  • the content ratio of the resin other than the acrylic urethane resin and the olefin resin in the resin composition (y) is smaller. preferable.
  • the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin is preferably less than 30 parts by weight, more preferably 20 parts by weight with respect to 100 parts by weight of the total amount of the resin contained in the resin composition (y). Less than 10 parts by weight, more preferably less than 10 parts by weight, even more preferably less than 5 parts by weight, and 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 And a solvent-free resin composition (y1) that does not contain a solvent. In the solventless resin composition (y1), no solvent is added, but the energy beam polymerizable monomer contributes to the improvement of the plasticity of the oligomer.
  • Mw mass average molecular weight
  • the mass average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 20,000 to 40. 3,000, more preferably 3,000 to 35,000, and still more preferably 4,000 to 30,000.
  • oligomer As said oligomer, what is necessary is just to have an ethylenically unsaturated group whose mass mean molecular weight is 50,000 or less among resin contained in the above-mentioned resin composition (y). Polymer (UP) is preferred. As the oligomer, a modified olefin resin having an ethylenically unsaturated group can also be used.
  • the total content of the oligomer and the energy beam polymerizable monomer in the solventless resin composition (y1) is preferably 50 to 100% 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, and still more preferably 70 to 85% by mass.
  • Examples of the energy ray polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, 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- And heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam. These energy beam polymerizable monomers may be used independently and may use 2 or more types together.
  • the mixing ratio of the oligomer to the energy beam polymerizable monomer is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, and still more preferably 35/65. ⁇ 80/20.
  • the solventless resin composition (y1) is further blended with a photopolymerization initiator.
  • a photopolymerization initiator By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with a relatively low energy beam.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol. Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned. These photoinitiators may be used independently and may use 2 or more types together.
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass with respect to the total amount (100 parts by mass) of the oligomer and energy beam polymerizable monomer.
  • the amount is preferably 0.02 to 3 parts by mass.
  • Non-expandable base material layer (Y2) Examples of the material for forming the non-intumescent base material layer (Y2) constituting the base material (Y) include paper materials, resins, metals, and the like, which are appropriately selected depending on the use of the laminate of one embodiment of the present invention. You can choose.
  • the non-expandable substrate layer (Y2) side of the expandable substrate layer (Y1) when the thermally expandable particles contained in the expandable substrate layer (Y1) expand, the non-expandable substrate layer (Y2) side of the expandable substrate layer (Y1) from the viewpoint of preferentially forming irregularities on the surface of the expandable substrate layer (Y1) on the pressure-sensitive adhesive layer (V1) side by suppressing the formation of irregularities on the surface of the non-expandable substrate layer (Y2) preferably has such rigidity that it does not deform due to expansion of the thermally expandable particles.
  • the storage elastic modulus E ′ (t) of the non-expandable base material layer (Y2) at the temperature (t) at the start of expansion of the thermally expandable particles is 1.1 ⁇ 10 7 Pa or more. It is preferable.
  • Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfate 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, poly Polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resin such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resin such as poly
  • These forming materials may be composed of one kind or in combination of two or more kinds.
  • a non-intumescent substrate layer (Y2) using two or more kinds of forming materials in combination a paper film is laminated with a thermoplastic resin such as polyethylene, and a metal film is formed on the surface of a resin film or sheet containing the resin. And the like.
  • a method for forming the metal layer for example, the above metal is deposited by a PVD method such as vacuum deposition, sputtering, or ion plating, or a metal foil made of the above metal is attached using a general adhesive. And the like.
  • the non-expandable base layer (Y2) contains a resin
  • the non-expandable base layer Also on the surface of (Y2) similarly to the above-mentioned expandable base material layer (Y1), a surface treatment by an oxidation method, a concavo-convex method, an easy adhesion treatment, or a primer treatment may be performed.
  • the non-intumescent base material layer (Y2) contains a resin
  • it may contain the above-mentioned base material additive that can be contained in the resin composition (y) together with the resin.
  • a non-expandable base material layer (Y2) is a non-expandable layer judged based on the above-mentioned method. Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) calculated from the above formula is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume. More preferably, it is less than 0.1 volume%, More preferably, it is less than 0.01 volume%.
  • a non-expandable base material layer (Y2) may contain a thermally expansible particle.
  • a resin contained in the non-expandable base material layer (Y2) it is possible to adjust the volume change rate to the above range even if the heat-expandable particles are contained.
  • the non-expandable base material layer (Y2) does not contain thermally expandable particles.
  • the content is preferably as small as possible.
  • the non-expandable base material layer (Y2) Is less than 3% 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, and still more preferably 0%. Less than 0.001% by mass.
  • the pressure-sensitive adhesive layer (V) of the support layer (II) used in one embodiment of the present invention can be formed from a pressure-sensitive adhesive composition (v) containing a pressure-sensitive resin.
  • the pressure-sensitive adhesive composition (v) may contain pressure-sensitive adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
  • pressure-sensitive adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
  • the first pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2) can also be formed from the pressure-sensitive adhesive composition (v) containing the following components.
  • the resin alone is preferably a polymer having adhesiveness and a mass average molecular weight (Mw) of 10,000 or more.
  • the mass 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 1,500,000, and even more preferably 30,000, from the viewpoint of improving adhesive force. ⁇ 1 million.
  • the adhesive resin examples include 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. In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
  • the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
  • the curable resin layer I As the first pressure-sensitive adhesive layer (V1-1) or (V1) in contact with) contains an acrylic resin, irregularities are formed on the surface of the first pressure-sensitive adhesive layer (V1-1) or (V1). It can be made easy.
  • the content of the acrylic resin in the adhesive resin is preferably from 30 to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (v) or the adhesive layer (V). 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 adhesive resin is preferably 35 to 100 with respect to the total amount (100% by mass) of the active ingredients of the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V).
  • the mass is 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 (v) preferably further contains a cross-linking agent when it contains a pressure-sensitive adhesive resin having a functional group.
  • the said crosslinking agent reacts with the adhesive resin which has a functional group, and bridge
  • crosslinking agent examples include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents may be used independently and may use 2 or more types together. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
  • the content of the crosslinking agent is appropriately adjusted depending on the number of functional groups that the adhesive resin has, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group, The amount is more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition (v) 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 a functional resin.
  • the weight average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and still more preferably 800 to 5,000.
  • Examples of the tackifier are obtained by copolymerizing C5 fractions such as rosin resin, terpene resin, styrene resin, pentene, isoprene, piperine, 1,3-pentadiene generated by thermal decomposition of petroleum naphtha.
  • C9 petroleum resin obtained by copolymerizing C9 fractions such as indene generated by thermal decomposition of petroleum naphtha and vinyltoluene, and hydrogenated resins obtained by hydrogenating these.
  • the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and further preferably 70 to 150 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • a tackifier may be used independently and may use 2 or more types from which a softening point, a structure, etc. differ. And when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.
  • the content of the tackifier is preferably 0.01 to the total amount (100% by mass) of the active ingredient in the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V). It is 65% by mass, 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 (v) contains an additive for pressure-sensitive adhesives used for general pressure-sensitive adhesives in addition to the above-mentioned additives, as long as the effects of the present invention are not impaired. You may do it.
  • 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.
  • the content of each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. ⁇ 10 parts by mass.
  • the 2nd adhesive layer (V2) which is an expandable adhesive layer Is formed from the above-mentioned pressure-sensitive adhesive composition (v) and the expandable pressure-sensitive adhesive composition (v22) further containing thermally expandable particles.
  • the thermally expandable particles are as described above.
  • the content of the heat-expandable particles is preferably based on the total amount (100% by mass) of the active ingredient of the expandable pressure-sensitive adhesive composition (v22) or the total mass (100% by mass) of the expandable pressure-sensitive adhesive layer. 1 to 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 (v) that is a material for forming the non-expandable pressure-sensitive adhesive layer may not contain thermally expandable particles. preferable. When the thermally expandable particles are contained, the content is preferably as small as possible.
  • a support layer having a first pressure-sensitive adhesive layer (V1-1) and a second pressure-sensitive adhesive layer (V1-2), which are non-intumescent pressure-sensitive adhesive layers.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (V1-1), 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 7 Pa or less, and even more preferably 1.0 ⁇ 10 7 Pa or less.
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer is 1.0 ⁇ 10 8 Pa or less, for example, the laminate shown in FIG.
  • the first pressure-sensitive adhesive that is in contact with the cured resin layer (I ′) due to the expansion of the thermally expandable particles in the expandable base material layer (Y1) by the heat expansion treatment when configured as 2a and 2b Unevenness is easily formed on the surface of the layer (V1-1). As a result, it is possible to obtain a laminate that can be easily separated in a lump with a slight force at the interface P between the support layer (II) and the cured resin layer (I ′).
  • the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 ⁇ 10 4 Pa or more, and more preferably Is 5.0 ⁇ 10 4 Pa or more, more preferably 1.0 ⁇ 10 5 Pa or more.
  • the light transmittance at a wavelength of 365 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 further preferably 70% or more.
  • the curing degree of the curable resin layer (I) is further improved when the curable resin layer (I) is irradiated with energy rays (ultraviolet rays) via the support layer (II).
  • the upper limit of the light transmittance at a wavelength of 365 nm is not particularly limited, but can be, for example, 95% or less.
  • the substrate (Y) and the pressure-sensitive adhesive layer (V) included in the support layer (II) preferably do not contain a colorant.
  • the content is preferably as small as possible, and is based on the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition (v) or the total mass (100% by mass) of the pressure-sensitive adhesive layer (V).
  • the content of the colorant is preferably less than 1% by mass with respect to the total amount (100% by mass) of the active ingredients of the resin composition (y) or the total mass (100% by mass) of the substrate (Y).
  • it is less than 0.1 mass%, More preferably, it is less than 0.01 mass%, More preferably, it is less than 0.001 mass%.
  • sealing object examples of the sealing object placed on a part of the surface of the curable resin layer (I) include a semiconductor chip, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, a panel substrate, and the like. Is mentioned.
  • a semiconductor chip with a cured resin layer can be manufactured by using the warp preventing laminate of one embodiment of the present invention.
  • a conventionally known semiconductor chip can be used as the semiconductor chip, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface.
  • a semiconductor chip is mounted so that the back surface on the opposite side to a circuit surface may be covered with the surface of a thermosetting resin layer. In this case, the circuit surface of the semiconductor chip is exposed after placement.
  • a known device such as a flip chip bonder or a die bonder can be used. The layout and number of semiconductor chips may be determined as appropriate according to the target package form, number of production, and the like.
  • the laminate for warpage prevention can be produced by the following method. First, a curable resin layer (I) is formed on a release film by applying and drying a curable resin composition. When the curable resin layer (I) is composed of two layers, each curable resin composition is formed on a separate release film and laminated so that both layers are in direct contact with each other. A resin layer is produced. The first curable resin composition is coated on the release film and dried to form the first curable resin layer (X1-1). Next, the first curable resin layer (X1-1) is formed on the release film. A laminated curable resin layer can also be produced by applying and drying the second curable resin layer (X1-2) or (X2).
  • the support layer (II) is formed by applying and drying the pressure-sensitive adhesive composition on the release film to form the pressure-sensitive adhesive layer (V), and then applying the resin material constituting the base material layer to the pressure-sensitive adhesive layer. It can be produced by coating and drying on top or attaching a sheet-like base material to the pressure-sensitive adhesive layer to form the base material layer.
  • the base material layer is composed of a plurality of layers
  • the resin material constituting the second base material layer is applied and dried on the first base material layer, and then the second base material layer is formed.
  • the base material layer is formed.
  • the pressure-sensitive adhesive composition is applied and dried on the second base material layer to form the second pressure-sensitive adhesive layer.
  • the first aspect of the method for producing a cured encapsulant of the present invention is a method for producing a cured encapsulant using the laminate of one aspect of the present invention, comprising the following steps (i) to (iv): Have.
  • FIG. 6 is a schematic cross-sectional view showing a process for producing a cured encapsulant with a cured resin layer, and more specifically, a cured encapsulant using a warp-preventing laminate 1a shown in FIG. 1 (b). It is the cross-sectional schematic diagram which showed the process of manufacturing. Hereinafter, each process described above will be described with reference to FIG. 6 as appropriate.
  • FIG. 6A shows a state where the adhesive surface of the pressure-sensitive adhesive layer (V1) of the support layer (II) is attached to the support 50 using the warp-preventing laminate 1b
  • FIG. These show a mode that the sealing target object 60 is mounted in a part of surface of curable resin layer (I).
  • 6 shows an example in which the laminate 1b shown in FIG. 1B is used.
  • the support is similarly used. Then, the warp preventing laminate and the sealing object are laminated or placed in this order.
  • the temperature condition in step (i) is preferably performed at a temperature at which the thermally expandable particles do not expand.
  • a temperature at which the thermally expandable particles do not expand For example, in an environment of 0 to 80 ° C. (however, the expansion start temperature (t) is 60 to 80 ° C. In some cases, it is preferable to be performed in an environment less than the expansion start temperature (t).
  • the support is preferably attached to the entire pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (V1) of the laminate. Therefore, the support is preferably plate-shaped. Moreover, as shown in FIG. 6, it is preferable that the area of the adhesive surface of the adhesive layer (V1) and the surface of the support on the side to be attached is equal to or larger than the area of the adhesive surface of the adhesive layer (V1).
  • the material constituting the support depending on the type of sealing object, the type of sealing material used in step (ii), etc., considering the required properties such as mechanical strength and heat resistance, it is appropriate Selected.
  • Specific materials constituting the support include, for example, metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, polyimide resins, Examples thereof include resin materials such as polyamideimide resin; composite materials such as glass epoxy resin, and among these, SUS, glass, silicon wafer and the like are preferable.
  • Examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
  • Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).
  • the thickness of a support body is suitably selected according to the kind of sealing target object, the kind of sealing material used at process (ii), etc., Preferably it is 20 micrometers or more and 50 mm or less, More preferably, it is 60 micrometers or more. 20 mm or less.
  • examples of the sealing object placed on a part of the surface of the curable resin layer (I) include, for example, semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panels. Examples include substrates. In the following description, a case where a semiconductor chip is used as the sealing object 60 will be described as an example.
  • a semiconductor chip with a cured resin layer can be manufactured by using the stacked body of one embodiment of the present invention.
  • a conventionally known semiconductor chip can be used as the semiconductor chip, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface.
  • a semiconductor chip is mounted so that the back surface on the opposite side to a circuit surface may be covered with the surface of curable resin layer (I). In this case, the circuit surface of the semiconductor chip is exposed after placement.
  • a known device such as a flip chip bonder or a die bonder can be used for mounting the semiconductor chip.
  • the layout and number of semiconductor chips may be determined as appropriate according to the target package form, number of production, and the like.
  • the surface of the curable resin layer (I) of this embodiment (in the example of FIG. 6, the surface of the non-expandable thermosetting resin layer (X1) opposite to the support layer (II)) is curable.
  • the adhesive strength of the semiconductor chip 60 is bonded to the surface of the curable resin layer (I)
  • the semiconductor chip 60 is bonded to the surface of the curable resin layer (I). It is fixed securely, and it becomes easy to prevent displacement.
  • a region larger than the chip size is covered with a sealing material, such as FOWLP and FOPLP, so that not only the circuit surface of the semiconductor chip but also the sealing material is used.
  • a sealing material such as FOWLP and FOPLP
  • the semiconductor chip is placed on a part of the surface of the curable resin layer (I), and the plurality of semiconductor chips are placed on the surface in a state where they are aligned at a predetermined interval.
  • the plurality of semiconductor chips be mounted on the surface in a state where they are arranged in a matrix of a plurality of rows and a plurality of columns with a certain interval. The interval between the semiconductor chips may be determined as appropriate according to the form of the target package.
  • ⁇ Process (ii)> In the step (ii), the sealing object placed on the curable resin layer (I) and the first surface of the curable resin layer (I) at least around the sealing object are heated. Cover with a curable sealing material (hereinafter also referred to as “coating treatment”). In the coating process, first, the sealing object and at least the peripheral part of the sealing object on the surface of the curable resin layer (I) are covered with a sealing material. Specifically, as shown in FIG. 6C, a laminated body 1b that is affixed on a support 50 and on which a semiconductor chip 60 that is an object to be sealed is placed on the curable resin layer (I) is provided. The molding die 70 is disposed so as to be positioned in the molding die 70.
  • the sealing material is injected through the injection hole 71 into the forming space 72 formed between the forming die 70, the laminate 1 b and the sealing object 60.
  • the sealing material fills the gaps between the plurality of semiconductor chips while covering the entire exposed surface of the semiconductor chip 60 that is the object to be sealed.
  • the sealing material 80 is injected into the molding space 72 using a resin molding method in which a resin material is injected into a mold, represented by the transfer molding method, the curable resin (I)
  • the flow of the sealing material 80 is generated in the direction along the surface (see the arrow in FIG. 6C).
  • the sealing object 60 is fixed by the curable resin layer (I), and the shear strength of the curable resin layer (I) with respect to the measurement adherend is described above. Thus, it becomes easy to prevent the sealing object 60 from being displaced or inclined.
  • the sealing material has a function of protecting the object to be sealed and its accompanying elements from the external environment.
  • the sealing material 80 used in the manufacturing method of one embodiment of the present invention is a thermosetting sealing material containing a thermosetting resin.
  • the sealing material may be a solid such as a granule, a pellet, or a film at room temperature, or a liquid in the form of a composition. From the viewpoint of workability, a sealing resin film that is a film-like sealing material is preferable.
  • a coating method besides the transfer molding method, it can be appropriately selected and applied according to the type of the sealing material from methods applied in the conventional sealing process, for example, a roll laminating method.
  • a vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a compression molding mold method, or the like can be applied.
  • the encapsulant after the coating treatment is thermally cured to form a cured encapsulant including an object to be encapsulated.
  • the curable resin layer (I) is also cured to form the cured resin layer (I ′).
  • a cured sealing body 85 in which the semiconductor chip 60 that is an object to be sealed is covered with the cured sealing material 81 by curing the sealing material 80. Get. As a result, the semiconductor chip 60 is protected by the hard material while maintaining the layout.
  • thermosetting resin layer (X1) is used as the curable resin layer (I)
  • the curing start temperature of the thermosetting sealing material 80 starts to be cured.
  • generation of the hardened thermosetting resin layer (X1 ')) can be advanced simultaneously. Therefore, in these cases, the number of heating steps for curing can be reduced, and the manufacturing process can be simplified.
  • the difference of the shrinkage stress between the two surfaces of the obtained cured sealing body 85 can be made small, and hardening is carried out. Warpage generated in the sealing body 85 can be effectively suppressed.
  • thermosetting the thermosetting resin layer (X1) simultaneously with the thermosetting of the encapsulant the difference in shrinkage stress between the two surfaces of the cured encapsulant 85 is reduced even in the curing process. And warpage is more effectively suppressed.
  • the heating temperature for curing in step (iii) is lower than the heating temperature for expansion in step (iv).
  • FIG. 6 (f) shows that the expandable base material layer (Y 1) becomes an expanded expandable base material layer (Y 1 ′) by the process of expanding the thermally expandable particles, and the cured resin layer (I ′) and the support expanded. The state separated at the interface with the layer (II ′) is shown. As shown in FIG.
  • the sealing body 200 can be obtained.
  • the presence of the cured resin layer (I ′) has a function capable of effectively suppressing the warpage generated in the cured sealed body, and contributes to the improvement of the reliability of the sealed object.
  • the “expansion treatment” in the step (iv) is a treatment for expanding the thermally expandable particles by heating at an expansion start temperature (t) or higher, and the support layer on the cured resin layer (I ′) side by the treatment. Unevenness occurs on the surface of (II). As a result, the separation can be easily performed at the interface P with a slight force.
  • the “temperature higher than the expansion start temperature (t)” for expanding the thermally expandable particles is preferably “expansion start temperature (t) + 10 ° C.” or higher and “expansion start temperature (t) + 60 ° C.” or lower. It is more preferable that the expansion start temperature (t) + 15 ° C.
  • the cured encapsulant 200 with a cured resin layer thus obtained is further subjected to necessary processing.
  • the cured resin layer as the warp correction layer is removed by grinding or the like while the semiconductor device is finally manufactured, and does not remain in the final semiconductor device.
  • the second aspect of the method for producing a cured encapsulant of the present invention is a method for producing a cured encapsulant using the laminate of one aspect of the present invention, which comprises the following steps (i ′) to (iv): Have Step (i ′): A part of the surface opposite to the first layer of the energy ray curable resin layer (X2), which is the first surface of the curable resin layer of the laminate for warpage prevention, Place the object to be sealed. Step (ii ′)-1: The energy beam curable resin layer (X2) is cured by irradiating energy beams.
  • Step (ii ′)-2 The object to be sealed and the first surface of the curable resin layer at least in the periphery of the object to be sealed are covered with a thermosetting sealing material.
  • FIG. 7 (a) shows that the curable resin layer (I) has a thermosetting resin layer (X1-1) on the support layer (II) side and an energy ray curable property on the side opposite to the support layer (II).
  • the state where the adhesive surface of the pressure-sensitive adhesive layer (V1) of the support layer (II) is stuck to the support 50 using the warp-preventing laminate 5 (see FIG. 5) consisting of the resin layer (X2) is shown in FIG. 7 (b) shows a state in which the sealing object 60 is placed on a part of the surface of the curable resin layer (I).
  • the surface of the curable resin layer (I) of the present embodiment (in the example of FIG. 7, the surface opposite to the support layer (II) of the energy ray curable resin layer (X2)) is curable.
  • the adhesive strength is that the first surface is attached to a glass plate at a temperature of 70 ° C., and the curable resin layer (I) is peeled off at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling speed of 300 mm / min.
  • the measured value is 1.7 N / 25 mm or more, the sealing object 60 is surely secured when the sealing object 60 is bonded to the surface of the curable resin layer (I). It is fixed, and it becomes easy to prevent positional deviation including tilt deviation.
  • Step (ii ′)-1 irradiates the energy ray curable resin layer (X2) with energy rays to form a cured resin layer (I * ) formed by curing the energy ray curable resin layer (X2). It is a process to do.
  • FIG. 7C is partially cured by forming a cured energy beam curable resin layer (X2 ′) by curing the energy beam curable resin layer (X2) in this step ( That is, it shows a state in which a cured resin layer (I * ) in which the first surface side layer is cured) is formed.
  • the type of energy beam and the irradiation conditions are not particularly limited as long as the energy beam curable resin layer (X2) is cured to such an extent that it sufficiently exhibits its function. What is necessary is just to select suitably according to the process to perform.
  • an ultraviolet curable resin composition is used as a material constituting the energy ray curable resin layer (X2)
  • a wide range of materials can be selected, and it is easily available as an energy ray source for curing the composition. It is possible to use an ultraviolet irradiation device that is excellent in handleability.
  • the illuminance of the energy rays at the time of curing of the energy ray curable resin layer (X2) is preferably 4 to 280 mW / cm 2 , and the light amount of the energy rays at the time of curing is 3 to 1,000 mJ / cm 2. 2 is preferable.
  • step (iii ′) including thermosetting Prior to the step (iii ′) including thermosetting, irradiation of energy rays in the step (ii ′)-1 prevents the energy ray curable resin from being cleaved by heating and causing a curing reaction to proceed.
  • the curing reaction by the line can be efficiently advanced. Moreover, it can also prevent that the low molecular component (photopolymerization initiator etc.) contained in energy-beam curable resin volatilizes by heating, and contaminates a sealing target object.
  • the energy ray curable resin layer with energy rays prior to thermosetting the energy ray curable resin (X2) is prevented from being cured and contracted by heating for thermosetting, and the sealing resin. And the adhesiveness between the energy ray curable resin (X2) can be prevented from being lowered.
  • step (ii ′)-2 After the sealing object 60 is arranged and the energy beam curable resin layer (X2 ′) cured by irradiating the energy beam is formed, in step (ii ′)-2, FIG.
  • the sealing material 80 is injected using a molding die (not shown). At this time, although the flow of the sealing material is generated in the surface direction, the sealing object 60 is fixed by the cured energy ray curable resin layer (X2 ′) and is used for measuring the curable resin layer (I).
  • the silicon chip having a thickness of 350 ⁇ m with a mirror surface of 3 mm ⁇ 3 mm is used as the measurement adherend, and the mirror surface of the measurement adherend is cured at 130 gf for 1 second at a temperature of 70 ° C.
  • the sealing object 60 may be displaced or inclined by setting it to 20 N / (3 mm ⁇ 3 mm) or more. It becomes easy to prevent.
  • the encapsulant after the coating treatment is thermally cured to form a cured encapsulant including an object to be encapsulated.
  • the thermosetting resin layer (X1-1) is also cured to form a cured resin layer (X1-1 ′), and a cured resin layer (I ′) in which both the first layer and the second layer are cured is formed.
  • a cured sealing body 85 in which the sealing object 60 is covered with the cured sealing material 81 is obtained.
  • thermosetting resin layer (X1-1) is used as the curable resin layer (I)
  • the thermosetting sealing material 80 and the curing start temperature are set to the same level. If the curing start temperature is different, or by heating to a higher curing start temperature or higher, the sealing material and the thermosetting resin layer can be cured simultaneously by one heating. be able to.
  • FIG. 7 (f) shows that the expandable base material layer (Y1) becomes the expandable base material layer (Y1 ′) by the treatment for expanding the expandable particles, and the cured resin layer (I ′) and the expanded support layer (II ′). It shows a state of separation at the interface with).
  • the necessary processing is performed on the cured sealing body 201 with the cured resin layer.
  • the curable resin layer (I) refers to both the “energy ray curable resin layer (X2)” and the “thermosetting resin layers (X1-1), (X1-2)”. Shall mean.
  • the physical-property value in the following manufacture examples and Examples is a value measured by the following method.
  • ⁇ Minimum curing temperature of curable resin layer> A plurality of measurement samples are prepared in advance using the same composition, and each is set at a set temperature of 60 ° C. to 20 ° C. using a differential scanning calorimeter (TA Instruments, Q2000). The time until the peak attributed to the curing reaction disappeared was measured. At this time, the temperature was raised from room temperature to the set temperature at a rate of temperature rise of 10 ° C./min. In the measurement, the temperature at which the curing reaction peak disappears in 2 hours was defined as the minimum curing temperature.
  • the expansion start temperature (t) of the thermally expandable particles used in each example was measured by the following method. To an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expandable particles to be measured is added, and an aluminum lid (diameter 5.6 mm, thickness 0. 1 mm) is prepared. Using a dynamic viscoelasticity measuring device, 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.
  • the displacement start temperature be the expansion start temperature (t).
  • the maximum expansion temperature refers to a temperature at which the displacement amount becomes maximum.
  • the amount of displacement obtained at the time of measuring the maximum expansion temperature is the thickness (Dm) of the support layer at the maximum expansion temperature. Further, the thickness (Da) of the support layer when each support layer is heated under the curing condition 1 (heating at 130 ° C. for 2 hours) of the curable resin layer and the curing condition 2 (at 160 ° C. of the curable resin layer). The thickness (Db) of the support layer when heated by heating for 1 hour was measured. And the value of (Da / Dm) * 100 and (Db / Dm) * 100 was calculated
  • thermosetting resin layer On the surface of the thermosetting resin layer formed on the release film, an adhesive tape (manufactured by Lintec Corporation, product name “PL Shin”) was laminated. Then, the release film was removed, and the surface of the exposed thermosetting resin layer was attached to the smooth surface of a glass plate (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Trading Co., Ltd.) as an adherend.
  • the application temperature of the thermosetting resin layer (X1) was 70 ° C.
  • the release materials used in the following production examples are as follows. Heavy release film: manufactured by Lintec Corporation, product name “SP-PET382150”, polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m
  • Light release film manufactured by Lintec Corporation, product name “SP-PET381031”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m
  • thermosetting resin layers of the warp preventing laminates of Examples 1 and 2 were respectively attached to a 12-inch thick 100 ⁇ m silicon wafer, and epoxy was applied to the opposite side of the thermosetting resin layer.
  • the resin composition was applied to a thickness of 30 ⁇ m.
  • the layer of the said epoxy resin composition and the thermosetting resin layer of each laminated body were heated and hardened.
  • a silicon wafer with a cured resin layer was placed on a horizontal table, and then visually observed, and the presence or absence of warpage was evaluated based on the following criteria.
  • B The amount of warpage is greater than 3 mm and less than 15 mm.
  • the amount of warpage is 15 mm or more.
  • the epoxy resin composition a mixture of “Epofix Resin” manufactured by Struers and a curing agent “Epofix Hardener” manufactured by the same company was used. In this evaluation, a silicon wafer with a large diameter is used as an adherend to simplify the experimental procedure, while an epoxy resin layer is provided on the back side of the adherend so that warpage is likely to occur. By doing so, the evaluation of warpage was made appropriate.
  • thermosetting resin layer On the release-treated surface of the light release film, the solution of the thermosetting resin composition prepared in (1) above is applied to form a coating film. It was dried at 120 ° C. for 2 minutes to form a thermosetting resin layer having a thickness of 25 ⁇ m. This is designated as a curable resin layer 1.
  • the adhesive force of the formed thermosetting resin layer 1 was 0.5 N / 25 mm.
  • Production Example 2 (1) Production of Support Layer Supporting a heat-peeling laminate (product name “NITTO 3195” manufactured by Nitto Denko Corporation) having a structure in which a heat-peeling adhesive layer is provided on a polyester film substrate. Used as a layer. This is designated as support layer 1.
  • the release liner provided in the surface of the heat-peeling adhesive layer was peeled off and used.
  • the support layer 1 has a pressure-sensitive adhesive layer containing a base material and thermally expandable particles, and the heat-expandable particles expand by being heated to an expansion start temperature of 170 ° C. or more, whereby the surface of the pressure-sensitive adhesive layer This produces a fine uneven shape.
  • the following isocyanate-based crosslinking agent (i) 5.0 parts by mass (solid)
  • the pressure-sensitive adhesive composition (2) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by mixing with water, diluting with toluene, and stirring uniformly.
  • 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 mass average molecular weight of 600,000.
  • the pressure-sensitive adhesive composition (1) prepared in Production Example 3 (1) is applied to the surface of the release layer of the light release film to form a coating film.
  • the coating film was dried at 100 ° C. for 60 seconds to form an adhesive layer (1) having a thickness of 5 ⁇ m.
  • (6) Formation of pressure-sensitive adhesive layer (2) The pressure-sensitive adhesive composition (2) prepared in Production Example 3 (2) is applied to the surface of the release layer of the above heavy release film to form a coating film.
  • the coating film was dried at 100 ° C. for 60 seconds to form an adhesive layer (2) having a thickness of 10 ⁇ m.
  • an anchor layer having a thickness of 40 ⁇ m.
  • an isocyanate-based crosslinking agent product name “Coronate L”, solid content concentration: 75% by mass, manufactured by Tosoh Corporation.
  • the resin composition containing the thermally expandable particles is applied onto the anchor layer to form a coating film, and the coating film is dried by heating at 100 ° C. for 2 minutes to a thickness of 35 ⁇ m. Formed.
  • the pressure-sensitive adhesive layer (1) was pasted on the thermally expandable layer.
  • a support layer having a release film laminated on the front and back was prepared. This is designated as support layer 2.
  • the support layer 2 has a base material including a pressure-sensitive adhesive layer and thermally expandable particles. When heated to 208 ° C. or higher, the thermally expandable particles expand, and the surface of the support layer has a fine uneven shape. Cause it to occur.
  • a support layer was prepared in the same procedure as in Production Example 3 except that the drying conditions after the change were changed to an atmospheric temperature of 100 ° C. for 1 minute. This is designated as support layer 3.
  • the support layer 3 has a base material including a pressure-sensitive adhesive layer and thermally expandable particles. When heated to 80 ° C. or higher, the thermally expandable particles expand, and a fine uneven shape is formed on the surface of the support layer. Cause it to occur.
  • a support layer was produced in the same procedure as in Production Example 3 except that the subsequent drying conditions were changed to an atmospheric temperature of 100 ° C. for 1 minute. This is referred to as a support layer 4.
  • the support layer 4 has a base material including a pressure-sensitive adhesive layer and thermally expandable particles. When heated to 100 ° C. or higher, the thermally expandable particles expand, and a fine uneven shape is formed on the surface of the support layer. Cause it to occur.
  • the drying temperature after applying the resin composition to form a coating film is set higher than the expansion start temperature (t) of the thermally expandable particles.
  • the drying temperature is an ambient temperature, no foaming was observed in the formed support layer.
  • a support layer was produced in the same procedure as in Production Example 3 except that the subsequent drying conditions were changed to an atmospheric temperature of 100 ° C. for 1 minute. This is referred to as a support layer 5.
  • the support layer 5 has a base material including a pressure-sensitive adhesive layer and heat-expandable particles, and the heat-expandable particles expand by being heated to 120 ° C. or higher, so that the surface of the support layer has a fine uneven shape. Cause it to occur.
  • Example 1 The release film laminated on the pressure-sensitive adhesive layer (2) of the support layer 2 produced in Production Example 3 is removed, and the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (2) exposed and the curability formed in Production Example 1 are obtained.
  • the surface of the resin layer 1 is laminated, and a heavy release film / adhesive layer (1) / base material / anchor layer / thermally expandable layer / adhesive layer (2) / thermosetting resin layer / release film in this order.
  • a laminated body for preventing warpage with a release film was obtained.
  • Example 2 The peeling film laminated
  • Example 1 As is clear from the results in Table 1, in Examples 1 and 2, when the curable resin layer was cured at 130 ° C. for 2 hours, the peelability between the cured resin layer and the support layer was good, and the warping Occurrence was sufficiently suppressed. In Examples 1 and 2, even when the curable resin layer was cured at 160 ° C. for 1 hour, the peelability between the cured resin layer and the support layer was maintained at a level that would not interfere with practical use, and the occurrence of warping was sufficiently suppressed. It had been. In particular, in Example 2, the support layer was foamed to some extent by curing at 160 ° C., and the peelability of the support layer was slightly lowered. In Example 1, both the peelability and warpage were evaluated as 130.

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Abstract

L'invention concerne un corps multicouche pouvant empêcher le gauchissement d'un corps étanche durci, qui comprend une couche de résine durcissable (I) comprenant une couche de résine thermodurcissable (X1) et une couche de support (II) portant la couche de résine durcissable (I); et qui est conçue de sorte que : la couche de résine durcissable (I) présente une surface adhésive ayant des propriétés adhésives; la couche de support (II) comprend un matériau de base (Y) et une couche adhésive (V); le matériau de base (Y) et/ou la couche adhésive (V) contiennent des particules thermiquement expansibles; la couche de résine durcissable (I), la couche adhésive (V) et le matériau de base (Y) sont disposées de manière séquentielle dans cet ordre; la surface adhésive de la couche de résine durcissable (I) se trouve sur le revers de la couche adhésive (V); la température de durcissement la plus basse (T1), à laquelle le durcissement de la couche de résine durcissable (I) est achevée en 2 heures formant ainsi une couche de résine durcie (I'), est inférieure à la température de début de moussage (T2) des particules thermiquement expansibles; et l'étanchéité est conférée à un objet à étanchéifier, au moyen de la surface adhésive de la couche de résine durcissable (I).
PCT/JP2018/036813 2018-03-30 2018-10-02 Corps multicouche pouvant empêcher le gauchissement d'un corps étanche durci et procédé de production d'un corps étanche durci WO2019187249A1 (fr)

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CN201880091676.2A CN111886309B (zh) 2018-03-30 2018-10-02 固化密封体的防翘曲用层叠体、以及固化密封体的制造方法
KR1020207015352A KR102576310B1 (ko) 2018-03-30 2018-10-02 경화 봉지체의 휨 방지용 적층체, 및 경화 봉지체의 제조 방법
JP2020509575A JP7240378B2 (ja) 2018-03-30 2018-10-02 硬化封止体の反り防止用積層体、及び、硬化封止体の製造方法

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PCT/JP2019/013490 WO2019189530A1 (fr) 2018-03-30 2019-03-28 Stratifié adhésif, procédé pour l'utilisation d'un stratifié adhésif, et procédé de production d'un corps étanche durci pourvu d'un film de résine durcie

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WO2022149602A1 (fr) * 2021-01-08 2022-07-14 昭和電工マテリアルズ株式会社 Composition de résine thermodurcissable, et dispositif de composant électronique

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