WO2020070790A1

WO2020070790A1 - Layered product and production method for cured sealing body

Info

Publication number: WO2020070790A1
Application number: PCT/JP2018/036812
Authority: WO
Inventors: 明徳佐藤; 洋佑高麗; 高志阿久津; 康彦垣内; 岡本　直也; 忠知山田; 中山　武人
Original assignee: リンテック株式会社
Priority date: 2018-10-02
Filing date: 2018-10-02
Publication date: 2020-04-09
Also published as: JPWO2020070790A1; KR20210044836A; KR102543787B1; CN112789334B; JP7129110B2; CN112789334A

Abstract

The present invention pertains to a layered product having an energy ray curable resin layer (I), and a support layer (II) which supports the energy ray curable resin layer (I), wherein the energy ray curable resin layer (I) has an adhesive surface, the support layer (II) has a substrate (Y) and an adhesive layer, at least the substrate (Y) and the adhesive layer contains thermally expandable particles, and the support layer (II) and a cured resin layer (I') obtained by curing the energy ray curable resin layer (I) are separated at the boundary therebetween, by a process of expanding the thermally expandable particles.

Description

Manufacturing method of laminated body and cured sealing body

The present invention relates to a method for producing a laminate and a cured sealing body.

In recent years, electronic devices have become smaller, lighter, and more sophisticated, and semiconductor chips are sometimes mounted in packages close to their size. Such a package is sometimes called a CSP (Chip Scale Package). Examples of the CSP include a WLP (Wafer Level Package) that is completed by processing the wafer size to the final package process, and a PLP (Panel Level Package) that is processed and completed by the panel size larger than the wafer size until the final package process. .

WLP and PLP are classified into a fan-in type and a fan-out type. In a fan-out type WLP (hereinafter, also referred to as “FOWLP”) and a PLP (hereinafter, also referred to as “FOLP”), a semiconductor chip is covered with a sealing material so as to have an area larger than the chip size. And a rewiring layer and external electrodes are formed not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material.

FOWLP and FOPLP are, for example, a placing step of placing a plurality of semiconductor chips on a temporary fixing sheet, a covering step of covering with a thermosetting sealing material, and a thermosetting curing of the sealing material. A curing step of obtaining a sealed body, a separation step of separating the cured sealed body and the temporary fixing sheet, and a rewiring layer forming step of forming a rewiring layer on the exposed semiconductor chip side surface, (Hereinafter, the processing performed in the coating step and the curing step is also referred to as “sealing processing”).

Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting electronic components, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a substrate. In the production of FOWLP and FOPLP, use of the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 is also conceivable.

Japanese Patent No. 3594853

However, when a cured sealing body is manufactured using the pressure-sensitive adhesive sheet described in Patent Document 1 as a temporary fixing sheet, the cured sealing body tends to warp due to heat shrinkage. This is because the semiconductor chip sealed in the cured sealing body is unevenly located on the surface side in contact with the temporary fixing sheet. A region where the ratio is relatively high and a region where the presence ratio of the cured resin having a large thermal expansion coefficient is relatively high occur, and a stress is generated due to a difference in the thermal shrinkage ratio between the two regions. Conceivable. This problem tends to become more pronounced as the package size increases, such as FOWLP and FOPLP.
The warped cured sealing body is, for example, easily cracked when the cured sealing body is ground in the next step, and is cured by the arm when the cured sealing body is transported by the device. A harmful effect may occur, such as an inconvenience during the delivery of the body.

As a method of suppressing the warpage of the cured sealing body, for example, a method of using a laminate including a temporary fixing layer provided with a thermally expandable pressure-sensitive adhesive layer containing thermally expandable particles and a thermosetting resin layer is also considered. Can be That is, a mounting step and a covering step of the semiconductor chip are performed on the thermosetting resin layer provided in the laminate, and thereafter, the thermosetting resin layer and the sealing material are heat-cured to form a cured seal with the cured resin layer. After obtaining the stationary body, the thermally expandable particles are expanded to separate the cured sealing body with the cured resin layer from the temporary fixing layer. According to this method, since the cured resin layer functions as a warp preventing layer of the cured sealing body, a cured sealing body in which the occurrence of warpage is suppressed can be obtained.

On the other hand, according to the above method, the treatment for expanding the thermally expandable particles and the treatment for curing the thermosetting resin layer are both heat treatments, so that the thermosetting resin layer is cured. In some cases, the heat-expandable particles in the temporary fixing layer are foamed during the heat treatment. According to the study of the present inventors, before the thermosetting resin layer is sufficiently cured, if the thermally expandable particles in the temporary fixing layer expand, the separability of the temporary fixing layer deteriorates in the subsequent separation step. Is known.
Therefore, it is possible to easily separate the cured resin layer and the temporary fixing layer after forming the cured sealing body with the cured resin layer while applying the cured resin layer as the warpage prevention layer to the cured sealing body. There is a need for a laminate that can be used to produce a cured encapsulant.

In view of the above problems, the present invention has a support layer and a curable resin layer, and can perform sealing by fixing an object to be sealed to the surface of the curable resin layer. A laminated body which can provide a cured resin layer as a warpage preventing layer to a cured sealing body formed by processing, and can easily separate the cured resin layer and the support layer, and the laminated body It is an object of the present invention to provide a method for producing a cured sealing body using the same.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the following problems can be solved by the present invention, and have completed the present invention.
That is, the present invention relates to the following [1] to [11].
[1] an energy ray-curable resin layer (I),
A support layer (II) for supporting the energy ray-curable resin layer (I),
The energy ray-curable resin layer (I) has a surface having tackiness,
The support layer (II) has a substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles;
A laminate in which a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) and a support layer (II) are separated at an interface thereof by a process of expanding the thermally expandable particles.
[2] The storage elastic modulus E ′ at 23 ° C. of the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) is 1.0 × 10 ⁷ to 1.0 × 10 ¹³ Pa. The laminate according to the above [1].
[3] The laminate according to the above [1] or [2], wherein the energy ray-curable resin layer (I) has a thickness of 1 to 500 μm.
[4] The laminate according to any one of the above [1] to [3], wherein the energy ray-curable resin layer (I) has a visible light transmittance of 5% or more.
[5] The laminate according to any one of the above [1] to [4], wherein the substrate (Y) has an expandable substrate layer (Y1) containing the thermally expandable particles.
[6] The laminate according to the above [5], wherein the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer.
[7] The laminate according to the above [5] or [6], wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.
[8] The base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1),
The support layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X) in this order,
The laminate according to any one of the above [5] to [7], wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.
[9] An object to be sealed is placed on a part of the surface of the energy ray-curable resin layer (I),
Irradiating the energy ray-curable resin layer (I) with energy rays to form a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I),
The object to be sealed and the surface of the cured resin layer (I ') at least in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material,
After the sealing material is thermally cured, the cured resin layer (I ′) and the support layer (II) are separated at the interface by a process of expanding the thermally expandable particles, and the object to be sealed is removed. The laminate according to any one of the above [1] to [8], which is used for forming a cured sealing body containing the same.
[10] The laminate according to the above [9], which is used to prevent the cured sealing body from warping.
[11] A method for producing a cured encapsulant using the laminate according to any one of the above [1] to [10], comprising the following steps (i) to (iv): Manufacturing method.
Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate. Step (ii): Applying the energy ray-curable resin layer (I). Step (iii) of forming a cured resin layer (I ′) obtained by irradiating an energy ray and curing the energy ray-curable resin layer (I): the sealing object and the sealing object At least the surface of the cured resin layer (I ′) at the peripheral portion is covered with a thermosetting sealing material, and the sealing material is thermoset to form a cured sealing body including the object to be sealed. Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by the treatment for expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer. Process

According to the present invention, it has a support layer and a curable resin layer, and can perform sealing by fixing an object to be sealed to the surface of the curable resin layer, and can be formed by the sealing. A laminated body that can provide a cured resin layer as a warpage preventing layer to the cured encapsulant, and can easily separate the cured resin layer and the support layer, and curing using the laminated body A method for manufacturing a sealed body can be provided.

FIG. 2 is a schematic cross-sectional view of the laminate, showing the configuration of the laminate of the first embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of the laminate showing the configuration of the laminate of the second embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of the laminate showing a configuration of the laminate of the third embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing a step of manufacturing a cured sealing body with a cured resin layer using the laminated body 1a shown in FIG. It is a cross-sectional schematic diagram which shows the processing method of a hardened sealing body.

In the present specification, whether or not a target layer is a “non-expandable layer” is determined by performing a process for expanding for 3 minutes, and then calculating a volume change rate before and after the process based on the following formula. Is less than 5%, it is determined that the layer is a “non-expandable layer”. On the other hand, when the volume change rate is 5% or more, it is determined that the layer is an “expandable layer”.
Volume change rate (%) = {(volume of the layer after treatment−volume of the layer before treatment) / volume of the layer before treatment} × 100
As the “treatment for expanding”, for example, in the case of a layer containing thermally expandable particles, a heat treatment may be performed at the expansion start temperature (t) of the thermally expandable particles for 3 minutes.

において In the present specification, the “active ingredient” refers to a component excluding a diluting solvent among components contained in a target composition.

In the present specification, the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically, a value measured based on the method described in Examples. It is.

において In this specification, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.

下限 In this specification, the lower limit and the upper limit described stepwise in a preferable numerical range (for example, a range such as the content) can be independently combined. 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.

Unless otherwise specified, each component and material exemplified in this specification may be used alone, or two or more may be used in combination. When two or more are used in combination, their combination may be used. And the ratio can be arbitrarily selected.

In the present specification, the “energy beam” means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include an ultraviolet ray, a radiation, and an electron beam. The ultraviolet light can be emitted by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet light source. The electron beam can be emitted from an electron beam generated by an electron beam accelerator or the like.
In the present specification, “energy ray-curable” means a property of being cured by irradiation with an energy ray, and “non-energy ray-curable” means a property of not being cured by irradiation of an energy ray. I do.

[Laminate]
The laminate of one embodiment of the present invention includes an energy-ray-curable resin layer (I) and a support layer (II) that supports the energy-ray-curable resin layer (I).
The energy ray-curable resin layer (I) has an adhesive surface.
The support layer (II) has a substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles.

The laminate of one embodiment of the present invention comprises a support for curing the energy ray-curable resin layer (I) by curing the heat-expandable particles in the support layer (II) and the cured resin layer (I ′). Layer (II) can be separated at its interface. In other words, in the laminate of one embodiment of the present invention, the heat-expandable particles expand the heat-expandable particles, and the surface of the layer containing the heat-expandable particles has irregularities. The contact area with the cured resin layer (I ′) obtained by curing the conductive resin layer (I) is reduced. As a result, at the interface between the support layer (II) and the cured resin layer (I ′), it can be easily and collectively separated with a small force.
Note that since the laminate of one embodiment of the present invention does not require heating when curing the energy ray-curable resin layer (I), the support layer is used when the energy ray-curable resin layer (I) is cured. The heat-expandable particles in (II) do not expand, and the separation property between the support layer (II) and the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) is excellent. It will be.

In the laminate of one embodiment of the present invention, an object to be sealed is placed on part of the surface of the energy ray-curable resin layer (I), and the energy ray-curable resin layer (I) is irradiated with energy rays. Forming a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I), and the sealing object and a cured resin layer (I ′) at least at a peripheral portion of the sealing object. Is coated with a thermosetting sealing material, and after the sealing material is thermoset, the cured resin layer (I ′) and the support layer (II) are expanded by expanding the thermally expandable particles. Is preferably used for separating a material at the interface to form a cured sealing body containing the object to be sealed.
The cured sealing body formed by the above method has the cured resin layer (I ′) on the surface on the side where the proportion of the semiconductor chips is relatively high. As a result, the 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.
That is, the laminate of one embodiment of the present invention is useful as a laminate for preventing warpage, which is used for preventing warpage of the cured sealing body.
At that time, since the laminate of one embodiment of the present invention includes the energy-ray-curable resin layer (I) which is easily adjusted to increase the adhesive strength more than the thermosetting resin layer, the object to be sealed is part of the surface. Can be fixed more reliably. In addition, when the thermosetting resin layer is heated at a high temperature, it is softened mainly in an initial stage of curing, which may cause a chip shift. Since it does not soften when cured by irradiation with rays, it is possible to avoid the occurrence of chip deviation due to the curing.

<Structure of laminate>
Next, a structure of a stack of one embodiment of the present invention will be described with reference to the drawings.
1 to 3 are schematic cross-sectional views of a laminate showing the configuration of the laminate according to the first to third embodiments of the present invention. In the following laminates according to the first to third aspects of the present invention, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X) (or the second pressure-sensitive adhesive layer (X2)) to be stuck to the support (that is, May be configured such that a release material is further laminated on the surface of the energy ray-curable resin layer (I) opposite to the support layer (II) side.

(Laminated body of the first embodiment)
The laminate of the first embodiment of the present invention includes the

laminates

1a and 1b shown in FIG.
Each of the

laminates

1a and 1b includes an energy ray-curable resin layer (I) and a support layer (II) having a substrate (Y) and an adhesive layer (X). It has a configuration in which a linear curable resin layer (I) is directly laminated.
In the laminate of the first aspect of the present invention, the adhesive surface of the adhesive layer (X) is attached to a support (not shown).

The support layer (II) contains thermally expandable particles in at least one of the layers, and in the laminate 1a, the base material (Y) is formed of an expandable base material layer containing thermally expandable particles ( This is a base material having a single-layer structure consisting only of Y1).
The base material (Y) may be a single-layered base material composed of only the expandable base material layer (Y1) as in a laminate 1a shown in FIG. 1 (a). As shown in the laminate 1b, a base material having a multilayer structure having an expandable base material layer (Y1) and a non-expandable base material layer (Y2) may be used. When the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2), the base material (Y) is an expandable base material layer (Y1) and a non-expandable base material layer ( Y2) alone.
Moreover, it is preferable that the expandable base material layer (Y1) and the non-expandable base material layer (Y2) have a configuration in which they are directly laminated.

In the laminate 1a shown in FIG. 1A, the thermal expansion particles contained in the expandable base material layer (Y1) expand due to the heat expansion treatment, and irregularities are generated on the surface of the base material (Y). The contact area with the cured resin layer (I ′) obtained by previously curing the line-curable resin layer (I) is reduced.
At this time, the adhesive surface of the adhesive layer (X) is attached to a support (not shown). When the pressure-sensitive adhesive layer (X) is sufficiently adhered to the support, the surface of the expansible base material layer (Y1) on the side of the pressure-sensitive adhesive layer (X) generates a force to generate irregularities. However, a repulsive force from the pressure-sensitive adhesive layer (X) is easily generated. Therefore, it is difficult to form irregularities on the surface of the base material (Y) on the side of the pressure-sensitive adhesive layer (X).
As a result, the laminate 1a can be easily and collectively separated with a small force at the interface P between the base material (Y) of the support layer (II) and the cured resin layer (I ').
In addition, by forming the pressure-sensitive adhesive layer (X) of the laminate 1a from a pressure-sensitive adhesive composition having a high adhesive force to the support, the pressure-sensitive adhesive layer can be more easily separated at the interface P.

In addition, from the viewpoint of suppressing transmission of the stress due to the thermally expandable particles to the pressure-sensitive adhesive layer (X) side, the base material (Y) is, as in the laminate 1b shown in FIG. It is preferable to have a material layer (Y1) and a non-expandable base material layer (Y2).
Since the stress due to the expansion of the thermally expandable particles of the expandable base material layer (Y1) is suppressed by the non-expandable base material layer (Y2), it is difficult for the stress to be transmitted to the pressure-sensitive adhesive layer (X).
Therefore, the surface of the pressure-sensitive adhesive layer (X) on the support side is unlikely to have irregularities, and the adhesion between the pressure-sensitive adhesive layer (X) and the support hardly changes before and after the heat expansion treatment, and good adhesion is maintained. can do. Thereby, irregularities are easily formed on the surface of the expandable base material layer (Y1) on the side of the energy ray-curable resin layer (I), and as a result, the support layer (II) and the expandable base material layer (Y1) harden. At the interface P with the resin layer (I ′), it is possible to easily and collectively separate them with a small force.
In addition, like the laminated body 1b shown in FIG. 1B, the expandable base material layer (Y1) and the energy ray-curable resin layer (I) are directly laminated, and the non-expandable base material layer (Y2) is formed. It is preferable that the pressure-sensitive adhesive layer (X) is laminated on the surface opposite to the expandable base material layer (Y1).

(Laminated body of the second embodiment)
As the laminate according to the second embodiment of the present invention, there are

laminates

2a and 2b shown in FIG.
In the

laminates

2a and 2b, the pressure-sensitive adhesive layer (X) of the support layer (II) has a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), and the first pressure-sensitive adhesive layer (X1 ) And the second pressure-sensitive adhesive layer (X2) sandwich the substrate (Y), and the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (X1) is directly laminated with the energy ray-curable resin layer (I).
In the laminate of the second aspect of the present invention, the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown).

Also in the laminate of the second aspect of the present invention, it is preferable that the substrate (Y) has an expandable substrate layer (Y1) containing thermally expandable particles.
The base material (Y) may be a single-layer base material composed of only the expandable base material layer (Y1) as in a laminate 2a shown in FIG. 2 (a). Like the laminate 2b shown, the base material may be a multi-layered base material having an expandable base material layer (Y1) and a non-expandable base material layer (Y2).

However, as described above, from the viewpoint of obtaining a laminate that maintains good adhesion between the second pressure-sensitive adhesive layer (X2) and the support before and after the heat expansion treatment, as shown in FIG. It is preferable that the material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2).
In the case of using the base material (Y) having the expandable base material layer (Y1) and the non-expandable base material layer (Y2) in the laminate of the second embodiment, as shown in FIG. The first pressure-sensitive adhesive layer (X1) is laminated on the surface of the non-expandable base material layer (Y2) on the energy ray-curable resin layer (I) side of the non-expandable base material layer (Y2). It is preferable to have a configuration in which the second pressure-sensitive adhesive layer (X2) is laminated on the surface on the side opposite to (Y1).

In the laminate of the second aspect, the thermally expandable particles in the expandable base material layer (Y1) constituting the base material (Y) expand due to the heat expansion treatment, and Irregularities occur.
Then, the first adhesive layer (X1) is also pushed up by the unevenness generated on the surface of the expandable base material layer (Y1), and the unevenness is also formed on the adhesive surface of the first adhesive layer (X1). (1) The contact area between the pressure-sensitive adhesive layer (X1) and the cured resin layer (I ′) obtained by previously curing the energy ray-curable resin layer (I) is reduced. As a result, at the interface P between the first pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I ′), it can be easily and collectively separated with a small force.
In addition, in the laminate of the second embodiment of the present invention, from the viewpoint of making the laminate easily separable at once at the interface P with a smaller force, the expansion of the base material (Y) of the support layer (II) It is preferable that the conductive base material layer (Y1) and the first pressure-sensitive adhesive layer (X1) are directly laminated.

(Laminated body of the third embodiment)
As a laminate according to the third embodiment of the present invention, a laminate 3 shown in FIG. 3 is exemplified.
The laminate 3 shown in FIG. 3 has a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, on one surface side of a substrate (Y). A support layer (II) having a second pressure-sensitive adhesive layer (X2), which is a non-expandable pressure-sensitive adhesive layer, is provided on the other surface side of Y), and the first pressure-sensitive adhesive layer (X1) and the energy ray-curable resin layer (I) is directly laminated.
In the laminate 3, the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown).
In addition, it is preferable that the base material (Y) which the laminated body of the 3rd aspect of this invention has is comprised from a non-expandable base material layer.

In the laminate according to the third aspect of the present invention, the thermally expandable particles in the first pressure-sensitive adhesive layer (X1), which is the expandable pressure-sensitive adhesive layer, expand due to the heat expansion treatment, and the first pressure-sensitive adhesive layer (X1) Irregularities occur on the surface, and the contact area between the first pressure-sensitive adhesive layer (X1) and the cured resin layer (I ′) obtained by previously curing the energy ray-curable resin layer (I) decreases.
On the other hand, since the base material (Y) is laminated on the surface of the first pressure-sensitive adhesive layer (X1) on the base material (Y) side, unevenness is unlikely to occur.
Therefore, the heat-expansion treatment tends to form irregularities on the surface of the first pressure-sensitive adhesive layer (X1) on the side of the energy-ray-curable resin layer (I), and as a result, the first pressure-sensitive adhesive layer of the support layer (II) ( At the interface P between the X1) and the cured resin layer (I ′), it can be easily and collectively separated with a small force.

The laminate of one embodiment of the present invention may be composed of only the support layer (II) and the energy ray-curable resin layer (I), and the support layer (II) and the energy ray-curable resin layer (I) It may have another layer other than the above. Examples of other layers include, for example, an adhesive layer provided on the surface of the energy ray-curable resin layer (I) on the side opposite to the support layer (II).
In addition, the laminate of one embodiment of the present invention preferably does not include a thermosetting resin layer from the viewpoint that heating is not required as much as possible in steps other than the heat expansion treatment. However, the thermosetting resin layer here means a layer that has thermosetting properties and is non-energy ray curable.

<Various physical properties of laminate>
(Peeling force (F ₀ ))
Before the energy ray-curable resin layer (I) is cured and before the heat expansion treatment, the support layer (II) and the support layer (II) are fixed from the viewpoint of sufficiently fixing the object to be sealed so as not to adversely affect the sealing operation. It is preferable that the adhesion to the energy ray-curable resin layer (I) is high.
In view of the above, in the laminate of one embodiment of the present invention, the support layer (II) and the energy-ray-curable resin layer (I) before the energy-ray-curable resin layer (I) is cured and before the thermal expansion treatment is performed. The separation force (F ₀ ) at the time of separation at the interface P is preferably 100 mN / 25 mm or more, more preferably 130 mN / 25 mm or more, still more preferably 160 mN / 25 mm or more, and preferably 50,000 mN / 25 mm. It is as follows.
The peeling force (F ₀ ) is a value measured by the following measuring method.
<Measurement of peeling force (F ₀ )>
After the laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name “PL Synth”) was applied to the surface of the energy ray-curable resin layer (I). )).
Next, the support layer (II) side of the laminate is attached to a glass plate (float plate glass, 3 mm (JISR 3202 product) manufactured by Yuko Shokai Co., Ltd.) via an adhesive. Next, the end of the glass plate to which the laminate is attached is fixed to a lower chuck of a universal tensile tester (manufactured by Orientec Co., Ltd., product name “Tensilon UTM-4-100”).
Subsequently, the adhesive tape and the support layer (II) are fixed by the upper chuck of the universal tensile tester so as to be separated at the interface P between the support layer (II) and the energy ray-curable resin layer (I) of the laminate. . Then, under the same environment as above, the peeling force measured when peeling off at the interface P by the 180 ° peeling method at a tensile speed of 300 mm / min based on JIS Z 0237: 2000 is referred to as “peeling force (F ₀ ) ".

(Peeling force (F ₁ ))
In the laminate of one embodiment of the present invention, after the energy ray-curable resin layer (I) is cured to form a cured resin layer (I ′), the support layer (II) and the cured resin layer (I) are subjected to heat expansion treatment. The separation force (F ₁ ) at the time of separation at the interface P with the ′) is usually 2000 mN / 25 mm or less, preferably 1000 mN / It is 25 mm or less, more preferably 500 mN / 25 mm or less, more preferably 150 mN / 25 mm or less, further preferably 100 mN / 25 mm or less, even more preferably 50 mN / 25 mm or less, and most preferably 0 mN / 25 mm.
When the peeling force (F ₁ ) is 0 mN / 25 mm, even if an attempt is made to measure the peeling force, it may be impossible to measure because the peeling force is too small.
The peeling force (F ₁ ) is a value measured by the following measuring method.
<Measurement of peeling force (F ₁ )>
After the laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name) was applied to the surface of the energy ray-curable resin layer (I) of the laminate. "PL thin") is attached.
Next, the support layer (II) side of the laminate is adhered to a glass plate (float plate glass, 3 mm (JIS R 3202), manufactured by Yuko Shokai Co., Ltd.) via an adhesive.
Next, ultraviolet rays are irradiated three times under the conditions of illuminance of 215 mW / cm ² and light amount of 187 mJ / cm ² to cure the energy ray-curable resin layer (I) to form a cured resin layer (I ′). Then, the glass plate and the laminate are heated at the maximum expansion temperature for 3 minutes to expand the thermally expandable particles in the expandable base material layer (Y1) of the laminate. Thereafter, in the same manner as the measurement of the peeling force (F ₀ ) described above, the peeling force measured when peeling off at the interface P between the support layer (II) and the cured resin layer (I ′) under the above conditions is determined. This is referred to as “peeling force (F ₁ )”.
In the measurement of the peeling force (F ₁ ), when the support layer (II) of the laminate was fixed with the upper chuck of the universal tensile tester, the cured resin layer (I ′) was completely separated at the interface P. When fixing is not possible, the measurement is terminated, and the peeling force (F ₁ ) at that time is set to “0 mN / 25 mm”.

(Adhesive strength of adhesive layer (X))
In the laminate of one embodiment of the present invention, the pressure-sensitive adhesive layer (X) (first pressure-sensitive adhesive layer (X1) and second pressure-sensitive adhesive layer (X2)) of the support layer (II) at room temperature (23 ° C.). The adhesive strength is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, and even more preferably 0.5 to N / 25 mm. ～ 4.0 N / 25 mm.
When the support layer (II) has the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), the adhesive strength of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is respectively Although it is preferable that it is the said range, from a viewpoint of improving the adhesiveness with a support body, and separating easily and collectively at the interface P, the 2nd adhesive layer (X2) of a support body and a 2nd adhesive layer adhered. It is more preferable that the adhesive strength is higher than the adhesive strength of the first adhesive layer (X1).

(Adhesive strength of energy ray-curable resin layer (I))
In the laminate of one embodiment of the present invention, from the viewpoint of improving the adhesion to the object to be sealed, the energy ray-curable resin layer (I) has a surface on which the object to be sealed is placed (that is, The surface opposite to the support layer (II)) has tackiness.
Specifically, at room temperature (23 ° C.), the adhesive strength of the surface of the energy ray-curable resin layer (I) on the side on which the object to be sealed is placed is determined from the viewpoint of sufficiently fixing the object to be sealed. It is preferably at least 0.05 N / 25 mm, more preferably at least 0.10 N / 25 mm, even more preferably at least 0.50 N / 25 mm. The upper limit of the adhesive force of the surface is not particularly limited, but is usually 50 N / 25 mm or less, may be 40 N / 25 mm or less, or may be 30 N / 25 mm or less.

In the present specification, these adhesive forces are values measured by the following measuring method.
<Measurement of adhesive strength>
A 50 μm-thick PET film (product name “Cosmoshine A4100”, manufactured by Toyobo Co., Ltd.) is laminated on the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) formed on the release film.
Then, the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) is affixed to a stainless steel plate (SUS304 No. 360 polished), which is an adherend, at 23 ° C. and 50% RH (relative humidity). After standing for 24 hours under the environment, the adhesive force at 23 ° C. is measured under the same environment according to JIS Z0237: 2000 by a 180 ° peeling method at a pulling speed of 300 mm / min.

(Probe tack value of substrate (Y))
The substrate (Y) of the support layer (II) is a non-adhesive substrate.
In one embodiment of the present invention, the determination as to whether or not the substrate is a non-adhesive substrate is performed when the probe tack value measured according to JISZ 0237: 1991 with respect to the surface of the target substrate is less than 50 mN / 5 mmφ. If so, the substrate is determined to be a “non-adhesive substrate”. On the other hand, if the probe tack value is 50 mN / 5 mmφ or more, the base material is determined to be “adhesive base material”.
The probe tack value on the surface of the substrate (Y) included in the support layer (II) used in one embodiment of the present invention is generally less than 50 mN / 5 mmφ, preferably less than 30 mN / 5 mmφ, and more preferably less than 10 mN / 5 mmφ. , More preferably less than 5 mN / 5 mmφ.
The probe tack value on the surface of the substrate (Y) is a value measured by the following measurement method.
<Measurement of probe tack value>
A test sample is obtained by cutting a substrate to be measured into a square having a side of 10 mm and leaving it to stand at 23 ° C. and an environment of 50% RH (relative humidity) for 24 hours. In a 23 ° C., 50% RH (relative humidity) environment, the probe tack value on the surface of the test sample was measured using a tacking tester (manufactured by Nippon Tokuseki Co., Ltd., product name “NTS-4800”) according to JIS. It is measured according to Z0237: 1991. Specifically, after a stainless steel probe having a diameter of 5 mm was brought into contact with the surface of the test sample for 1 second at a contact load of 0.98 N / cm ² , the probe was contacted at a speed of 10 mm / sec. The force required to separate from the surface is measured, and the obtained value is used as the probe tack value of the test sample.

Next, each layer included in the laminate of one embodiment of the present invention will be described.

<Support layer (II)>
The support layer (II) included in the laminate of one embodiment of the present invention includes a base (Y) and an adhesive layer (X), and at least one of the base (Y) and the adhesive layer (X) is provided. It contains thermally expandable particles. As described above, the support layer (II) is a layer separated from the energy-ray-curable resin layer (I), which is a support target, by a thermal expansion treatment, and is a layer that plays a role as a so-called temporary fixing layer. .
The support layer (II) used in one embodiment of the present invention includes a case where the layer containing the thermally expandable particles is included in the configuration of the base material (Y) and a case where the layer is included in the configuration of the pressure-sensitive adhesive layer (X). Is divided into the following modes.
-The support layer (II) of the first embodiment: a support layer (II) including a base material (Y) having an expandable base material layer (Y1) containing thermally expandable particles.
The support layer (II) of the second embodiment: a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing heat-expandable particles, on both sides of the substrate (Y), and a non-expandable pressure-sensitive adhesive A support layer (II) having a second pressure-sensitive adhesive layer (X2) as a layer.

[Supporting layer (II) of first embodiment]
As the support layer (II) of the first embodiment, as shown in FIGS. 1 and 2, the base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles.
In the support layer (II) of the first embodiment, the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer, from the viewpoint of easily and collectively separating at a small force at the interface P.
Specifically, in the support layer (II) of the

laminates

1a and 1b shown in FIG. 1, the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer.
In the support layer (II) of the

laminates

2a and 2b shown in FIG. 2, both the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are non-expandable pressure-sensitive adhesive layers. Preferably, there is.
As in the case of the support layer (II) of the first embodiment, since the base material (Y) has the expandable base material layer (Y1), the pressure-sensitive adhesive layer (X) does not need to have the expandability, and the expandability is reduced. It is not restricted by the composition, composition and process for application. In this way, when designing the pressure-sensitive adhesive layer (X), for example, it is possible to perform a design that prioritizes desired performance other than expandability such as performance such as adhesiveness, productivity, economy, and the like. (X) The design flexibility can be improved.

The thickness of the substrate (Y) of the support layer (II) of the first embodiment before the heat expansion treatment is preferably from 10 to 1000 μm, more preferably from 20 to 700 μm, further preferably from 25 to 500 μm, and still more preferably from 30 to 30 μm. ３００300 μm.

The thickness of the pressure-sensitive adhesive layer (X) of the support layer (II) of the first embodiment before the heat expansion treatment is preferably 1 to 60 μm, more preferably 2 to 50 μm, still more preferably 3 to 40 μm, and still more preferably. It is 5 to 30 μm.

In the present specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of pressure-sensitive adhesive layers (X), the “thickness of the pressure-sensitive adhesive layer (X)” It means the thickness of each pressure-sensitive adhesive layer (in FIG. 2, each thickness of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2)).
Further, in the present specification, the thickness of each layer constituting the laminate means a value measured by the method described in Examples.

In the support layer (II) of the first embodiment, the thickness ratio [(Y1) / (X)] between the expandable base material layer (Y1) and the pressure-sensitive adhesive layer (X) before the heat expansion treatment is as follows. It is preferably at most 1,000, more preferably at most 200, further preferably at most 60, even more preferably at most 30.
When the thickness ratio is 1000 or less, a laminate that can be easily and collectively separated with a small force at the interface P between the support layer (II) and the cured resin layer (I ′) by the heat expansion treatment is provided. can do.
In addition, the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1.0 or more, and still more preferably 5.0 or more.

Further, in the support layer (II) of the first embodiment, the base material (Y) may be composed of only the expandable base material layer (Y1) as shown in FIG. As shown in FIG. 1 (b), it has an expandable base material layer (Y1) on the energy ray-curable resin layer (I) side and a non-expandable base material layer (Y2) on the adhesive layer (X) side. May be provided.

In the support layer (II) of the first embodiment, the thickness ratio [(Y1) / (Y2)] between the expandable base material layer (Y1) and the non-expandable base material layer (Y2) before the heat expansion treatment. Is preferably 0.02 to 200, more preferably 0.03 to 150, and still more preferably 0.05 to 100.

[Supporting layer (II) of second embodiment]
As the support layer (II) of the second embodiment, as shown in FIG. 3, a first pressure-sensitive adhesive layer, which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, is provided on both sides of the substrate (Y). One having (X1) and a second pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer.
In the support layer (II) of the second embodiment, the first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer, and the energy ray-curable resin layer (I) are in direct contact.
In the support layer (II) of the second embodiment, the substrate (Y) is preferably a non-expandable substrate. It is preferable that the non-expandable base material is composed of only the non-expandable base material layer (Y2).

In the support layer (II) of the second embodiment, the first pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer before the heat expansion treatment. The thickness ratio ((X1) / (X2)) is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.

In the support layer (II) of the second embodiment, the thickness ratio of the first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer, to the base material (Y) before the heat expansion treatment [(X1) / (Y)] is preferably from 0.05 to 20, more preferably from 0.1 to 10, and even more preferably from 0.2 to 3.

Hereinafter, after describing the heat-expandable particles contained in any of the layers constituting the support layer (II), the expansible base material layer (Y1) constituting the base material (Y) and the non-expandable base material The layer (Y2) and the pressure-sensitive adhesive layer (X) will be described in detail.

(Thermally expandable particles)
As the heat-expandable particles used in one embodiment of the present invention, any particles may be used as long as they are expanded by a predetermined heat expansion process.
The average particle size of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 3 to 100 μm, more preferably 4 to 70 μm, further preferably 6 to 60 μm, and still more preferably 10 to 100 μm. 50 μm.
The average particle diameter of the thermally expandable particles before expansion is a volume median particle diameter (D ₅₀ ), and is a laser diffraction particle size distribution analyzer (for example, product name “Master Sizer 3000” manufactured by Malvern). In the particle distribution of the heat-expandable particles before expansion, which is measured by using, the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion corresponds to a particle size corresponding to 50%.

The 90% particle diameter (D ₉₀ ) of the thermally expandable particles before expansion at 23 ° C. used in one embodiment of the present invention is preferably 10 to 150 μm, more preferably 20 to 100 μm, and still more preferably 25 to 90 μm. Even more preferably, it is 30 to 80 μm.
The 90% particle diameter (D ₉₀ ) of the thermally expandable particles before expansion is measured using a laser diffraction type particle size distribution analyzer (for example, product name “Master Sizer 3000” manufactured by Malvern). In the particle distribution of the heat-expandable particles before, it means a particle diameter whose cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion corresponds to 90%.

The thermally expandable particles used in one embodiment of the present invention may be particles that do not expand when the sealing material is cured and have an expansion start temperature (t) higher than the curing temperature of the sealing material. It is preferable that the thermal expansion particles have an expansion start temperature (t) adjusted to 60 to 270 ° C. The expansion start temperature (t) is appropriately selected according to the curing temperature of the sealing material to be used.
Further, in the present specification, the expansion start temperature (t) of the thermally expandable particles means a value measured based on the method described in Examples.

As the heat-expandable particles, a microencapsulated foaming agent comprising an outer shell made of a thermoplastic resin, and an inner component contained in the outer shell and vaporized when heated to a predetermined temperature. Preferably, there is.
Examples of the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include a vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.

Examples of the internal components included in the outer shell include, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane , Cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, iso Hexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isonanodecane, , 6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane and the like. .
These inclusion components may be used alone or in combination of two or more.
The expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of the inclusion component.

The maximum volume expansion coefficient of the heat-expandable particles used in one embodiment of the present invention when heated to a temperature equal to or higher than the expansion start temperature (t) is preferably 1.5 to 100 times, more preferably 2 to 80 times, and furthermore Preferably it is 2.5 to 60 times, more preferably 3 to 40 times.

<Expandable base material layer (Y1)>
The expandable base material layer (Y1) included in the support layer (II) used in one embodiment of the present invention is a layer that contains thermally expandable particles and can be expanded by a predetermined heat expansion treatment.

In addition, from the viewpoint of improving the interlayer adhesion between the expandable base material layer (Y1) and another layer to be laminated, the surface of the expandable base material layer (Y1) is oxidized, surface-roughened, or the like. Treatment, easy adhesion treatment, or primer treatment may be performed.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet method), hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of the unevenness method include a sand blast method and a solvent treatment method. And the like.

In one embodiment of the present invention, the expandable base material layer (Y1) preferably satisfies the following requirement (1).
-Requirement (1): The storage elastic modulus E '(t) of the expandable base material layer (Y1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 × 10 ⁷ Pa or less.
In the present specification, the storage elastic modulus E ′ of the expandable base material layer (Y1) at a predetermined temperature means a value measured by the method described in Examples.

The requirement (1) can be said to be an index indicating the rigidity of the expandable base material layer (Y1) immediately before the expansion of the thermally expandable particles.
In order to enable easy separation with a small force at the interface P between the support layer (II) and the cured resin layer (I ′), the support layer ( It is necessary to make it easy to form irregularities on the surface on the side laminated with the energy ray-curable resin layer (I) of (II).
That is, in the expandable base material layer (Y1) satisfying the requirement (1), the thermally expandable particles expand at the expansion start temperature (t) and become sufficiently large, and the energy ray-curable resin layer (I) is Irregularities are likely to be formed on the surface of the support layer (II) on the side where the coating is formed.
As a result, a laminate that can be easily separated with a small force at the interface P between the support layer (II) and the cured resin layer (I ′) can be obtained.

From the above viewpoint, the storage elastic modulus E ′ (t) of the expandable base material layer (Y1) defined by the requirement (1) is preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 × 10 ⁶ Pa. ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.
In addition, it suppresses the flow of the expanded thermally expandable particles, improves the shape retention of irregularities formed on the surface of the support layer (II) on the side where the energy ray-curable resin layer (I) is laminated, From the viewpoint that the separation can be performed more easily with a small force at the interface P, the storage elastic modulus E ′ (t) of the expandable base material layer (Y1), which is defined in the requirement (1), is preferably 1.0 ×. It is at least 10 ³ Pa, more preferably at least 1.0 × 10 ⁴ Pa, even more preferably at least 1.0 × 10 ⁵ Pa.

The expandable base material layer (Y1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.
In addition, the resin composition (y) may contain an additive for a base material, if necessary, as long as the effects of the present invention are not impaired.
Examples of the base material additive include a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, and the like.
In addition, these additives for base materials may be used independently, respectively, and may use 2 or more types together.
When these base material additives are contained, the content of each base material additive is preferably from 0.0001 to 20 parts by mass, more preferably from 0.001 to 20 parts by mass, based on 100 parts by mass of the resin. 10 parts by mass.

The content of the thermally expandable particles is preferably 1 to 40 with respect to the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the active ingredient of the resin composition (y). %, More preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass.

The resin contained in the resin composition (y) that is the material for forming the expandable base material layer (Y1) may be a non-adhesive resin or an adhesive resin.
That is, even if the resin contained in the resin composition (y) is an adhesive resin, in the process of forming the expandable base material layer (Y1) from the resin composition (y), the adhesive resin becomes polymerizable. It suffices that the resin obtained by a polymerization reaction with the compound becomes a non-adhesive resin and the expandable base material layer (Y1) containing the resin becomes non-adhesive.

The weight average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 700,000, and further preferably from 1,000 to 500,000.

When the resin is a copolymer having two or more types of structural units, the form of the copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer. It may be.

The content of the resin is preferably 50 to 99% by mass based on the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount of the active ingredients (100% by mass) of the resin composition (y). , More preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.

In addition, from a viewpoint of forming the expandable base material layer (Y1) satisfying the above requirement (1), the resin contained in the resin composition (y) is selected from acrylic urethane-based resins and olefin-based resins. Preferably, it contains more than one species.
The following resin (U1) is preferable as the acrylic urethane-based resin.
-An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylate.

(Acrylic urethane resin (U1))
Examples of the urethane prepolymer (UP) serving as the main chain of the acrylic urethane-based resin (U1) include a reaction product of a polyol and a polyvalent isocyanate.
The urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.

Examples of the polyol serving as a raw material of the urethane prepolymer (UP) include an alkylene type polyol, an ether type polyol, an ester type polyol, an ester amide type polyol, an ester ether type polyol, and a carbonate type polyol.
These polyols may be used alone or in combination of two or more.
The polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, or a carbonate diol, and further preferably an ester diol or a carbonate diol.

Examples of the ester type diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, One or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; and phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, and diphenylmethane-4 , 4'-Dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, heptic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexa Hydrophthalic acid, Condensed polymers of dicarboxylic acids such as hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, and one or more selected from anhydrides thereof are exemplified.
Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol and polyneo And pentyl terephthalate diol.

Examples of the alkylene type diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, Alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol;

Examples of the carbonate type diol include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, and 1,3-propylene carbonate diol. , 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol and the like.

Examples of the polyvalent isocyanate serving as a raw material of the urethane prepolymer (UP) include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate.
These polyvalent isocyanates may be used alone or in combination of two or more.
In addition, these polyvalent isocyanates may be a modified trimethylolpropane adduct, a modified buret reacted with water, or a modified isocyanurate containing an isocyanurate ring.

Among these, as the polyvalent isocyanate used in one embodiment of the present invention, diisocyanate is preferable, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 One or more selected from -tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate are more preferable.

Examples of the alicyclic diisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane Examples thereof include diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate, and isophorone diisocyanate (IPDI) is preferable.

In one embodiment of the present invention, the urethane prepolymer (UP) serving as the main chain of the acrylic urethane-based resin (U1) is a reaction product of a diol and a diisocyanate, and has a straight chain having an ethylenically unsaturated group at both terminals. Urethane prepolymers are preferred.
As a method for introducing an ethylenically unsaturated group into both terminals of the linear urethane prepolymer, a NCO group at a terminal of the linear urethane prepolymer obtained by reacting a diol with a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting

Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.

The vinyl compound serving as a side chain of the acrylic urethane resin (U1) contains at least a (meth) acrylate.
As the (meth) acrylic acid ester, one or more selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are preferable, and it is more preferable to use the alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate together.

When alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are used in combination, the mixing ratio of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 100 parts by mass. Preferably it is 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, even more preferably 1.5 to 10 parts by mass.

アルキル The alkyl group of the alkyl (meth) acrylate preferably has 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 3.

ヒドロキシ As the hydroxyalkyl (meth) acrylate, the same hydroxyalkyl (meth) acrylate used to introduce an ethylenically unsaturated group into both terminals of the above-mentioned linear urethane prepolymer can be used.

Examples of vinyl compounds other than (meth) acrylic acid esters include, for example, aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate , (Meth) acrylonitrile, N-vinylpyrrolidone, polar group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and meth (acrylamide).
These may be used alone or in combination of two or more.

The content of the (meth) acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, and still more preferably the total amount (100% by mass) of the vinyl compound. It is 80 to 100% by mass, more preferably 90 to 100% by mass.

The total content of the alkyl (meth) acrylate and the hydroxyalkyl (meth) acrylate in the vinyl compound is preferably from 40 to 100% by mass, more preferably from 65 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound. It is 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass.

In the acrylic urethane resin (U1) used in one embodiment of the present invention, the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (u12) derived from the vinyl compound [(u11 ) / (U12)] is preferably from 10/90 to 80/20, more preferably from 20/80 to 70/30, still more preferably from 30/70 to 60/40, and even more preferably 35 by mass ratio. / 65 to 55/45.

(Olefin resin)
The olefin-based resin suitable as the resin contained in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
The olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, and specific examples include ethylene, propylene, butylene, isobutylene, 1-hexene and the like.
Among these, ethylene and propylene are preferred.

Specific olefinic resins, for example, ultra low density polyethylene (VLDPE, density: 880 kg / ^{m 3} or more 910 kg / ^m less than ^3), low density polyethylene (LDPE, density: 910 kg / ^{m 3} or more 915 kg / ^m less than ³ ), medium density polyethylene (MDPE, density: 915 kg / ^{m 3} or more 942kg / ^m less than ^3), high density polyethylene (HDPE, density: 942kg / ^{m 3} or higher), polyethylene resins such as linear low density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin-based elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); Vinyl alcohol copolymer (EVOH); ethylene-propylene Olefin terpolymers such as-(5-ethylidene-2-norbornene);

において In one embodiment of the present invention, the olefin-based resin may be a modified olefin-based resin further subjected to at least one modification selected from acid modification, hydroxyl group modification, and acrylic modification.

For example, as the acid-modified olefin resin obtained by subjecting the olefin resin to acid modification, a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof with the above-mentioned unmodified olefin resin. Is mentioned.
Examples of the above unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, and itaconic anhydride , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like.
The unsaturated carboxylic acids or their anhydrides may be used alone or in combination of two or more.

The acrylic-modified olefin-based resin obtained by subjecting the olefin-based resin to an acrylic modification is a modified olefin-based resin obtained by graft-polymerizing an alkyl (meth) acrylate as a side chain to the unmodified olefin-based resin as a main chain. Polymers.
The number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12.
Examples of the above-mentioned alkyl (meth) acrylate include the same compounds as the compounds that can be selected as the monomer (a1 ′) described below.

Examples of the hydroxyl group-modified olefin resin obtained by subjecting the olefin resin to hydroxyl group modification include a modified polymer obtained by graft-polymerizing a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin as a main chain.
Examples of the hydroxyl-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.

(Resins other than acrylic urethane resin and olefin resin)
In one embodiment of the present invention, the resin composition (y) may contain a resin other than the acrylic urethane resin and the olefin resin, as long as the effects of the present invention are not impaired.
Examples of 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; and acrylonitrile-butadiene-styrene copolymer. Polycarbonate; Polyether ether ketone; Polyether sulfone; Polyphenylene sulfide; Polyimide resin such as polyetherimide and polyimide; Polyamide resin; Acrylic resin; Fluorinated resins and the like can be mentioned.

However, from the viewpoint of forming the expandable base material layer (Y1) satisfying the above requirement (1), the smaller the content ratio of the resin other than the acrylic urethane resin and the olefin resin in the resin composition (y), the better. preferable.
The content ratio of the resin other than the acrylic urethane resin and the olefin resin is preferably less than 30 parts by mass, more preferably 20 parts by mass, based on 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than 10 parts by weight, more preferably less than 5 parts by weight, even more preferably less than 1 part by weight.

(Solvent-free resin composition (y1))
As the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray-polymerizable monomer, and the above-described thermally expandable particles are blended. And a solvent-free resin composition (y1) containing no solvent.
In the solventless resin composition (y1), no solvent is blended, but the energy ray polymerizable monomer contributes to the improvement of the plasticity of the oligomer.
By irradiating the coating film formed from the solvent-free resin composition (y1) with an energy ray, it is easy to form the expandable base material layer (Y1) satisfying the requirement (1).

種類 The type, shape and blending amount (content) of the thermally expandable particles blended in the solventless resin composition (y1) are as described above.

The weight average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and still more preferably 3,000 to 35,000, Still more preferably, it is 4000 to 30,000.

The oligomer may be any of the resins contained in the resin composition (y) described above, as long as the resin has an ethylenically unsaturated group having a weight average molecular weight of 50,000 or less. UP) is preferred.
In addition, a modified olefin-based resin having an ethylenically unsaturated group may be used as the oligomer.

The total content of the oligomer and the energy ray-polymerizable monomer in the solventless resin composition (y1) is preferably 50 to 50% based on the total amount (100% by mass) of the solventless resin composition (y1). It is 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, even more preferably 70 to 85% by mass.

Examples of the energy beam polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, and adamantane ( Alicyclic polymerizable compounds such as meth) acrylate and tricyclodecane acrylate; aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate and phenol-ethylene oxide modified acrylate; tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- Heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam.
These energy ray polymerizable monomers may be used alone or in combination of two or more.

The mixing ratio of the oligomer and the energy ray-polymerizable monomer (the oligomer / the energy ray-polymerizable monomer) is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, and still more preferably 35/65. ８０80/20.

In one embodiment of the present invention, the solvent-free resin composition (y1) preferably further contains a photopolymerization initiator.
By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with relatively low energy energy rays.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol Examples include nitrile, dibenzyl, diacetyl, 8-chloranthraquinone and the like.
These photopolymerization initiators may be used alone or in combination of two or more.

The compounding amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, based on the total amount (100 parts by mass) of the oligomer and the energy ray polymerizable monomer. Preferably it is 0.02 to 3 parts by mass.

<Non-expandable base material layer (Y2)>
As a material for forming the non-expandable base material layer (Y2) included in the base material (Y), for example, a paper material, a resin, a metal, or the like can be given. You can choose.

Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, parchment paper, glassine paper, and the like.
Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer; polyethylene terephthalate, Polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polysulfone; Polyether sulfone; Polyphenylene sulfide; Polyimide-based resin such as polyetherimide and polyimide; Polyamide-based resin; Acrylic resin; Tsu Motokei resin, and the like.
Examples of the metal include aluminum, tin, chromium, and titanium.

These forming materials may be composed of one type, or two or more types may be used in combination.
As the non-expandable base material layer (Y2) using two or more kinds of forming materials in combination, a paper material laminated with a thermoplastic resin such as polyethylene, or a metal film formed on the surface of a resin film or sheet containing the resin And the like.
In addition, as a method of forming the metal layer, for example, a method in which the metal is deposited by a PVD method such as vacuum evaporation, sputtering, or ion plating, or a metal foil made of the metal is attached using a general adhesive. And the like.

Here, in one embodiment of the present invention, when the expandable particles contained in the expandable base material layer (Y1) expand, the expandable base material layer (Y1) is closer to the non-expandable base material layer (Y2). From the viewpoint of suppressing the formation of irregularities on the surface and forming the irregularities predominantly on the surface of the expandable base material layer (Y1) on the side of the pressure-sensitive adhesive layer (X1), the non-expandable base material layer ( Y2) preferably has such a rigidity that it does not deform due to expansion of the expandable particles. Specifically, the storage elastic modulus E ′ (t) of the non-expandable base material layer (Y2) at the temperature (t) at the time when the expansion of the expandable particles starts is 1.1 × 10 ⁷ Pa or more. Is preferred.

In addition, from the viewpoint of improving interlayer adhesion between the non-expandable base material layer (Y2) and another layer to be laminated, when the non-expandable base material layer (Y2) contains a resin, the non-expandable base material layer The surface of (Y2) may be subjected to a surface treatment such as an oxidation method or a concavo-convex method, an easy adhesion treatment, or a primer treatment as in the case of the above-described expandable base material layer (Y1).

場合 In addition, when the non-expandable base material layer (Y2) contains a resin, the above-mentioned base material additive which may be contained in the resin composition (y) may be contained together with the resin.

The non-intumescent base material layer (Y2) is a non-intumescent layer determined based on the method described above.
Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) calculated from the above equation is less than 5%, preferably less than 2%, more preferably less than 1%, and still more preferably. Is less than 0.1%, even more preferably less than 0.01%.

In addition, the non-expandable base material layer (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range. For example, by selecting the 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 thermally expandable particles are contained.
However, it is preferable that the non-expandable base material layer (Y2) does not contain thermally expandable particles. When the non-expandable base material layer (Y2) contains heat-expandable particles, the content thereof is preferably as small as possible. Is usually 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, more preferably less than 0.01% by mass, based on the total amount (100% by mass). Less than 001% by mass.

<Adhesive layer (X)>
The pressure-sensitive adhesive layer (X) included in the support layer (II) used in one embodiment of the present invention can be formed from a pressure-sensitive adhesive composition (x) containing a pressure-sensitive adhesive resin.
Further, the pressure-sensitive adhesive composition (x) may contain a pressure-sensitive adhesive additive such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
Hereinafter, each component contained in the pressure-sensitive adhesive composition (x) will be described.
In addition, even when the support layer (II) has the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are also And the pressure-sensitive adhesive composition (x) containing the following components.

(Adhesive resin)
The pressure-sensitive adhesive resin used in one embodiment of the present invention is preferably a polymer having the pressure-sensitive adhesive alone and having a weight average molecular weight (Mw) of 10,000 or more.
The weight average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1.5,000,000, and still more preferably 30,000, from the viewpoint of improving the adhesive strength. ~ 1 million.

Specific adhesive resins include, for example, rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins.
These adhesive resins may be used alone or in combination of two or more.
When these adhesive resins are copolymers having two or more types of constituent units, the form of the copolymer is not particularly limited, and may be a block copolymer, a random copolymer, or a graft copolymer. Any of polymers may be used.

In one embodiment of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of developing excellent adhesive strength.
When the support layer (II) having the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is used, the first pressure-sensitive adhesive layer ( By including an acrylic resin in X1), it is possible to easily form irregularities on the surface of the first pressure-sensitive adhesive layer (X1).

The content of the acrylic resin in the adhesive resin is preferably 30 to 30% based on the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X). It is 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.

The content of the pressure-sensitive adhesive resin is preferably 35 to 100% by mass relative to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X). %, More preferably 50 to 100% by mass, still more preferably 60 to 98% by mass, and still more preferably 70 to 95% by mass.

(Crosslinking agent)
In one embodiment of the present invention, when the pressure-sensitive adhesive composition (x) contains a pressure-sensitive adhesive resin having a functional group, the pressure-sensitive adhesive composition (x) preferably further contains a crosslinking agent.
The crosslinking agent reacts with the adhesive resin having a functional group, and crosslinks the adhesive resins with the functional group as a crosslinking starting point.

Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, and a metal chelate-based crosslinking agent.
These crosslinking agents may be used alone or in combination of two or more.
Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoint of increasing the cohesive force to improve the adhesive strength and from the viewpoint of easy availability.

The content of the crosslinking agent is appropriately adjusted depending on the number of functional groups contained in the adhesive resin, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group. More preferably, it is 0.03 to 7 parts by mass, and still more preferably 0.05 to 5 parts by mass.

(Tackifier)
In one embodiment of the present invention, the pressure-sensitive adhesive composition (x) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
In the present specification, the “tackifier” is a component that assists in improving the adhesive strength of the above-mentioned adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, It is distinguished from the conductive resin.
The weight average molecular weight (Mw) of the tackifier is preferably 400 to 9000, more preferably 500 to 8000, and further preferably 800 to 5000.

Examples of the tackifier include rosin-based resins, terpene-based resins, styrene-based resins, and copolymers of C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene generated by thermal decomposition of petroleum naphtha. C5 petroleum resin obtained, a C9 petroleum resin obtained by copolymerizing a C9 fraction such as indene and vinyltoluene generated by thermal decomposition of petroleum naphtha, and a hydrogenated resin obtained by hydrogenating these.

The softening point of the tackifier is preferably from 60 to 170 ° C, more preferably from 65 to 160 ° C, and even more preferably from 70 to 150 ° C.
In the present specification, the “softening point” of the tackifier means a value measured according to JIS K 2531.
The tackifier may be used alone, or two or more kinds having different softening points and structures may be used in combination.
When two or more tackifiers are used, the weighted average of the softening points of the tackifiers preferably falls within the above range.

The content of the tackifier is preferably 0.01 to 65% based on the total amount of the active ingredient (100% by mass) of the pressure-sensitive adhesive composition (x) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X). %, More preferably 0.1 to 50% by mass, still more preferably 1 to 40% by mass, and still more preferably 2 to 30% by mass.

(Adhesive additive)
In one embodiment of the present invention, the pressure-sensitive adhesive composition (x) contains a pressure-sensitive adhesive additive used for a general pressure-sensitive adhesive, in addition to the additives described above, as long as the effects of the present invention are not impaired. It may be.
Examples of such adhesive additives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, and the like. Is mentioned.
These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
When these adhesive additives are contained, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 20 parts by mass, based on 100 parts by mass of the adhesive resin. １０10 parts by mass.

In addition, when the support layer (II) of the above-described second embodiment having the first pressure-sensitive adhesive layer (X1) that is an expandable pressure-sensitive adhesive layer is used, the first pressure-sensitive adhesive layer (X1) that is the expandable pressure-sensitive adhesive layer is used. The forming material is formed from the expandable pressure-sensitive adhesive composition (x11) further containing the heat-expandable particles in the pressure-sensitive adhesive composition (x) described above.
The thermally expandable particles are as described above.
The content of the heat-expandable particles is preferably 1 to 100% based on the total amount of the active ingredient (100% by mass) or the total amount (100% by mass) of the expandable pressure-sensitive adhesive composition (x11). It is 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass.

On the other hand, when the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition (x), which is a material for forming the non-expandable pressure-sensitive adhesive layer, preferably does not contain thermally expandable particles.
When heat-expandable particles are contained, the content is preferably as small as possible. The content is preferably based on the total amount of active ingredients (100% by mass) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive composition (x). On the other hand, it is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass.

Note that a support layer (II) having a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), which is a non-expandable pressure-sensitive adhesive layer, is used as in the

laminates

2a and 2b shown in FIG. In this case, the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁸ Pa or less, more preferably 5.0 × 10 ⁸ Pa or less. The pressure is 0 × 10 ⁷ Pa or less, more preferably 1.0 × 10 ⁷ Pa or less.
If the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1), which is a non-expandable pressure-sensitive adhesive layer, is 1.0 × 10 ⁸ Pa or less, for example, the

laminates

2a and 2b shown in FIG. In such a configuration, the first pressure-sensitive adhesive layer (X1) in contact with the cured resin layer (I ′) due to the expansion of the thermally expandable particles in the expandable base material layer (Y1) due to the heat expansion treatment. ) Is likely to form irregularities on the surface.
As a result, it is possible to obtain a laminate that can be easily and collectively separated at a small 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 (X1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁴ Pa or more, and more preferably 5.10 × 10 ⁴ Pa or more. 0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

The light transmittance at a wavelength of 375 nm of the support layer (II) included in the laminate of one embodiment of the present invention is preferably 30% or more, more preferably 50% or more, and still more preferably 70% or more. When the light transmittance is within the above range, when the energy ray-curable resin layer (I) is irradiated with energy rays (ultraviolet rays) via the support layer (II), the energy ray-curable resin layer (I) is cured. The degree is more improved. The upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, but can be, for example, 95% or less. The transmittance can be measured according to a known method using a spectrophotometer.
From the viewpoint of achieving the above light transmittance, when the substrate (Y) and the pressure-sensitive adhesive layer (X) of the support layer (II) contain a colorant, the effect of the present invention is not impaired. It is preferable to adjust the content.
When a coloring agent is contained, the content is preferably as small as possible. The content is based on the total amount of the active ingredient (100% by mass) or the total amount of the pressure-sensitive adhesive layer (X) (100% by mass). , Preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, even more preferably less than 0.001% by mass. The content of the coloring agent is preferably less than 1% by mass, more preferably less than 1% by mass, based on the total amount (100% by mass) of the active ingredients of the resin composition (y) or the total amount (100% by mass) of the base material (Y). It is less than 0.1% by mass, more preferably less than 0.01% by mass, even more preferably less than 0.001% by mass.

<Energy ray-curable resin layer (I)>
The energy ray-curable resin layer (I) is not particularly limited as long as it is a layer that can be cured by irradiating an energy ray. For example, the energy ray-curable resin composition containing the energy ray-curable component (a) Is formed.

[Energy ray-curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays.
As the energy ray-curable component (a), a polymer (a1) having an energy ray-curable double bond and having a mass average molecular weight (Mw) of 80,000 to 2,000,000 (hereinafter, also simply referred to as “polymer (a1)”) And a compound (a2) having an energy-ray-curable double bond and a molecular weight of 100 to 80,000 (hereinafter also simply referred to as “compound (a2)”).
The energy ray-curable component (a) may be used alone or in combination of two or more.

(Polymer (a1))
The polymer (a1) is a polymer having an energy ray-curable double bond and having a weight average molecular weight (Mw) of 80,000 to 2,000,000.
Examples of the polymer (a1) include an acrylic polymer (a11) having a functional group X capable of reacting with a group of another compound, a group Y reacting with the functional group X, and an energy ray-curable double. An acrylic resin (a1-1) obtained by polymerizing the energy ray-curable compound (a12) having a bond and the polymer is exemplified.
The polymer (a1) may be used alone or in combination of two or more.

・ Acrylic polymer (a11)
Examples of the functional group X of the acrylic polymer (a11) include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (in which one or two hydrogen atoms of an amino group are substituted with a group other than a hydrogen atom. Or an epoxy group.

Examples of the acrylic polymer (a11) include those obtained by copolymerizing an acrylic monomer having the functional group X and an acrylic monomer having no functional group X. Further, a monomer (non-acrylic monomer) other than the acrylic monomer may be copolymerized. The acrylic polymer (a11) may be a random copolymer or a block copolymer.
The acrylic polymer (a11) may be used alone or in combination of two or more.

Examples of the acrylic monomer having the functional group X include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturated compounds such as vinyl alcohol and allyl alcohol Alcohol (unsaturated alcohol having no (meth) acryloyl skeleton) and the like.
Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth) acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citraconic acid Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond); anhydrides of the above ethylenically unsaturated dicarboxylic acids; and carboxyalkyl (meth) acrylates such as 2-carboxyethyl methacrylate. .
Among these, a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.

Examples of the acrylic monomer having no functional group X include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( T) tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, Examples thereof include (meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure having 1 to 18 carbon atoms, such as octadecyl (meth) acrylate (stearyl (meth) acrylate).
Examples of the acrylic monomer having no functional group X include, for example, methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and the like. (Meth) acrylic acid esters having an aromatic group, including (meth) acrylic acid esters containing an alkoxyalkyl group of the following; aryl (meth) acrylic acid esters such as phenyl (meth) acrylate; non-crosslinkable (meth) Acrylamide and its derivatives; (meth) acrylates having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; No.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

In the acrylic polymer (a11), the content of the structural unit derived from the acrylic monomer having the functional group X is preferably from 0.1 to 50% by mass, based on the total amount of the structural units constituting the polymer. Preferably it is 1 to 40% by mass, more preferably 3 to 30% by mass. When the content of the structural unit is within the above range, the content of the energy ray-curable double bond in the obtained acrylic resin (a1-1) can be easily adjusted to a preferable range.

-Energy ray-curable compound (a12)
The energy ray-curable compound (a12) is a compound having a group Y that reacts with the functional group X and an energy ray-curable double bond.
Examples of the group Y include one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxy group, and among these, an isocyanate group is preferable. When the energy ray-curable compound (a12) has an isocyanate group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.
The number of energy beam-curable double bonds contained in the energy beam-curable compound (a12) is preferably 1 to 5, more preferably 1 to 3, in one molecule.
The energy ray-curable compound (a12) may be used alone or in combination of two or more.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meth-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate and 1,1- (bisacryloyloxymethyl) ethyl Isocyanate; acryloyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth) acrylate Acryloyl monoisocyanate compound. Among these, 2-methacryloyloxyethyl isocyanate is preferred.

In the acrylic resin (a1-1), the content of the energy ray-curable double bond derived from the energy ray-curable compound (a12) relative to the content of the functional group X derived from the acrylic polymer (a11) Is preferably 20 to 120 mol%, more preferably 5 to 100 mol%, and still more preferably 50 to 100 mol%. When the above ratio is in the above range, the adhesive strength of the cured resin layer (I ′) formed by curing becomes larger. When the energy ray-curable compound (a12) is a monofunctional compound (having one of the above groups in one molecule), the upper limit of the content is 100 mol%. When the curable compound (a12) is a polyfunctional compound (having two or more groups in one molecule), the upper limit of the content may exceed 100 mol%.

The content of the acrylic resin (a1-1) is based on the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , Preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and still more preferably 3 to 20% by mass.

質量 The weight average molecular weight (Mw) of the polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1500,000.

The polymer (a1) may be at least partially cross-linked by a cross-linking agent (e) described below, or may be non-cross-linked.

(Compound (a2))
Compound (a2) is a compound having an energy ray-curable double bond and a molecular weight of 100 to 80,000.
As the energy ray-curable double bond of the compound (a2), a (meth) acryloyl group, a vinyl group and the like are preferable.
Examples of the compound (a2) include a low molecular weight compound having an energy ray-curable double bond, an epoxy resin having an energy ray-curable double bond, and a phenol resin having an energy ray-curable double bond. .
The compound (a2) may be used alone or in combination of two or more.

Examples of the low molecular weight compound having an energy ray-curable double bond include polyfunctional monomers and oligomers, and an acrylate compound having a (meth) acryloyl group is preferable.
Examples of the acrylate compound include 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and 2,2-bis [4- ((Meth) acryloxypolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate (tricyclo Decandimethylol di (meth) acryl ), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy Bifunctional (meth) acrylates such as 1,3-di (meth) acryloxypropane; tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) Isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol Polyfunctional (meth) acrylates such as tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate; urethane (meth) acrylate Polyfunctional (meth) acrylate oligomer such as Goma like.

As the epoxy resin having an energy-ray-curable double bond and the phenol resin having an energy-ray-curable double bond, for example, those described in paragraph 0043 of JP-A-2013-194102 are used. be able to. Such a resin also corresponds to a resin constituting the thermosetting component (f) described later, but is handled as the compound (a2) in the present invention.

質量 The mass average molecular weight (Mw) of the compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.

The content of the compound (a2) is preferably 1% with respect to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). It is preferably from 40 to 40% by mass, more preferably from 2 to 30% by mass, and still more preferably from 3 to 20% by mass.

[Polymer (b) having no energy beam-curable double bond]
When the energy ray-curable resin composition contains the compound (a2), the energy ray-curable resin composition further contains a polymer (b) having no energy ray-curable double bond (hereinafter, also simply referred to as “polymer (b)”). Is preferred.
The polymer (b) may be used alone or in combination of two or more.

Examples of the polymer (b) include an acrylic polymer, a phenoxy resin, a urethane resin, a polyester, a rubber resin, an acrylic urethane resin, polyvinyl alcohol (PVA), a butyral resin, and a polyester urethane resin. Among these, an acrylic polymer (hereinafter, also referred to as “acrylic polymer (b-1)”) is preferable.

The acrylic polymer (b-1) may be a known one. For example, it may be a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include: (meth) acrylic acid alkyl ester, (meth) acrylic acid ester having a cyclic skeleton, glycidyl group-containing (meth) acrylic acid ester, and hydroxyl group (Meth) acrylic acid esters, substituted amino group-containing (meth) acrylic acid esters, and the like. Here, the “substituted amino group” is as described above.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid Undecyl, dodecyl (meth) acrylate (lauryl (meth) acrylate), (meth Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, (meth) ) Alkyl (meth) acrylates in which the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms, such as octadecyl acrylate (stearyl (meth) acrylate).

Examples of the (meth) acrylate having a cyclic skeleton include, for example, cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; benzyl (meth) acrylate and the like. Aralkyl (meth) acrylate; cycloalkenyl (meth) acrylate such as dicyclopentenyl (meth) acrylate; cycloalkenyloxyalkyl (meth) acrylate such as dicyclopentenyloxyethyl (meth) acrylate Esters and the like.

Examples of the glycidyl group-containing (meth) acrylate include glycidyl (meth) acrylate.
Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
Examples of the substituted amino group-containing (meth) acrylate include N-methylaminoethyl (meth) acrylate.

非 Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

The polymer (b) may be at least partially cross-linked by the cross-linking agent (e), or may be non-cross-linked.
The polymer (b) at least partially crosslinked by the crosslinking agent (e) includes, for example, a polymer in which a reactive functional group in the polymer (b) has reacted with the crosslinking agent (e).
The reactive functional group may be appropriately selected according to the type of the crosslinking agent (e) and the like, and is not particularly limited. For example, when the crosslinking agent (e) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group. High hydroxyl groups are preferred. When the crosslinking agent (e) is an epoxy compound, the reactive functional group includes, for example, a carboxy group, an amino group, an amide group and the like. Are preferred. However, it is preferable that the reactive functional group be a group other than a carboxy group from the viewpoint of preventing corrosion of circuits of the semiconductor wafer and the semiconductor chip.

重合 As the polymer (b) having the reactive functional group, for example, a polymer obtained by polymerizing at least the monomer having the reactive functional group can be mentioned. In the case of the acrylic polymer (b-1), any one or both of the acrylic monomer and the non-acrylic monomer described above as the monomer constituting the acrylic polymer (b-1) having the reactive functional group is used. It may be used. For example, as the polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester may be mentioned. Among acrylic monomers or non-acrylic monomers, there may be mentioned those obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the reactive functional group.

In the polymer (b), the content of the structural unit derived from the monomer having a reactive functional group is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, based on the total amount of the structural units constituting the polymer (b). is there. When the content of the structural unit is in the above range, the degree of crosslinking in the polymer (b) is in a more preferable range.

質量 The mass average molecular weight (Mw) of the polymer (b) is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1500,000, from the viewpoint that the film formability of the energy ray-curable resin composition becomes better.

Examples of the energy ray-curable resin composition include those containing one or both of the polymer (a1) and the compound (a2). When the resin composition contains the compound (a2), the polymer (b) is also used. It is preferred to contain.

The total content of the energy ray-curable component (a) and the polymer (b) is determined based on the total amount of the active components (100% by mass) of the energy ray-curable resin composition or the total amount of the energy ray-curable resin layer (I) ( 100% by mass), preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass. When the total content is within the above range, the energy ray curability becomes better.

When the energy ray-curable resin composition or the energy ray-curable resin layer (I) contains the energy ray-curable component (a) and the polymer (b), the content of the polymer (b) is The amount is preferably from 3 to 160 parts by mass, more preferably from 6 to 130 parts by mass, based on 100 parts by mass of the active ingredient (a). When the content of the polymer (b) is in the above range, the energy ray curability becomes better.

The energy ray-curable resin composition contains, in addition to the energy ray-curable component (a) and the polymer (b), a photopolymerization initiator (c), a coupling agent (d), and a crosslinking agent (e) according to the purpose. ), A coloring agent (g), a thermosetting component (f), a curing accelerator (g), a filler (h) and a general-purpose additive (z). Is also good. For example, by using an energy-ray-curable resin composition containing the energy-ray-curable component (a) and the thermosetting component (f), the formed energy-ray-curable resin layer (I) is coated by heating. The adhesive strength to the adherend is improved, and the strength of the cured resin layer (I ′) formed from the energy ray-curable resin layer (I) is also improved.

[Photopolymerization initiator (c)]
Examples of the photopolymerization initiator (c) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, and benzoin dimethyl ketal; Acetophenone compounds such as -hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfides such as benzylphenyl sulfide and tetramethylthiuram monosulfide Α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime Benzophenone compounds such as benzophenone compounds; peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methyl Vinyl) phenyl] propanone; 2-chloroanthraquino And the like. Also, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as an amine can be used.
The photopolymerization initiator (c) may be used alone or in combination of two or more.
The content of the photopolymerization initiator (c) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is preferably 0.1 to 100 parts by mass of the energy ray-curable compound (a). The amount is from 01 to 20 parts by mass, preferably from 0.03 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass.

[Coupling agent (d)]
By using a coupling agent (d) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesiveness of the energy ray-curable resin layer (I) can be improved. The cured resin layer (I ') obtained by curing the curable resin layer (I) has improved water resistance without impairing the heat resistance.
The coupling agent (d) may be used alone or in combination of two or more.

The coupling agent (d) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray-curable component (a), the polymer (b) or the like, and is preferably a silane coupling agent. More preferred.
Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino ) Propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyl methyl dimethoxy silane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, and the like.

The content of the coupling agent (d) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is 100 parts by mass in total of the energy ray-curable component (a) and the polymer (b). On the other hand, it is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass. When the content of the coupling agent (d) is equal to or more than the above lower limit, effects such as improvement in dispersibility of the filler in the resin and improvement in adhesiveness of the energy ray-curable resin layer (I) are more remarkably obtained. The generation of outgas is suppressed by being equal to or less than the upper limit.

[Crosslinking agent (e)]
By cross-linking the energy ray-curable component (a), the polymer (b), and the like using the cross-linking agent (e), the initial adhesive strength and cohesion of the energy ray-curable resin layer (I) can be adjusted.
The crosslinking agent (e) may be used alone or in combination of two or more.

Examples of the crosslinking agent (e) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based crosslinker (a crosslinker having a metal chelate structure), an aziridine-based crosslinker (a crosslinker having an aziridinyl group), and the like. Is mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively abbreviated as “aromatic polyvalent isocyanate compound, etc.”). Trimers, isocyanurates and adducts of the aromatic polyisocyanate compound, etc .; terminal isocyanate urethane prepolymers obtained by reacting the aromatic polyvalent isocyanate compound with a polyol compound, etc. Is mentioned.
The “adduct” is a mixture of the aromatic polyvalent isocyanate compound, the aliphatic polyvalent isocyanate compound or the alicyclic polyvalent isocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. It means a reaction product with a compound having a molecular active hydrogen, and examples thereof include an adduct of xylylene diisocyanate of trimethylolpropane as described later. Further, the “terminal isocyanate urethane prepolymer” means a prepolymer having a urethane bond and having an isocyanate group at the terminal of the molecule.

As the organic polyvalent isocyanate compound, more specifically, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane To all or some of the hydroxyl groups of polyols such as tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate. Two or more compounds are added; lysine diisocyanate.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane- Tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine and the like.

場合 When using an organic polyvalent isocyanate compound as the crosslinking agent (e), it is preferable to use a hydroxyl group-containing polymer as the energy ray-curable component (a) and / or the polymer (b). When the crosslinking agent (e) has an isocyanate group and the energy ray-curable component (a) and / or the polymer (b) has a hydroxyl group, the crosslinking agent (e) and the energy ray-curable component (a) and / or Alternatively, a crosslinked structure can be easily introduced into the energy ray-curable resin layer (I) by a reaction with the polymer (b).

The content of the crosslinking agent (e) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is based on 100 parts by mass of the total of the energy ray-curable component (a) and the polymer (b). The amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 5 parts by mass.

[Thermosetting component (f)]
Examples of the thermosetting component (f) include an epoxy thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, and a silicone resin. Of these, the epoxy thermosetting resin is preferable.
The thermosetting component (f) may be used alone or in combination of two or more.

(Epoxy thermosetting resin)
The epoxy-based thermosetting resin contains an epoxy resin (f1), and may further contain a thermosetting agent (f2).

Examples of the epoxy resin (f1) include known epoxy resins, and examples thereof include a polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolak epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin. Bifunctional or higher functional epoxy compounds such as resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.
The epoxy resin (f1) may be used alone or in combination of two or more.

As the epoxy resin (f1), an epoxy resin having an unsaturated hydrocarbon group such as an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a (meth) acryloyl group, a (meth) acrylamide group or the like is used. Is also good. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the obtained package is improved.

The number average molecular weight of the epoxy resin (f1) is preferably from 300 to 30,000, more preferably from the viewpoint of the curability of the energy ray-curable resin layer (I) and the strength and heat resistance of the cured resin layer (I ′). It is from 400 to 10,000, more preferably from 500 to 3,000.
The epoxy equivalent of the epoxy resin (f1) is preferably 100 to 1000 g / eq, more preferably 150 to 800 g / eq.

The thermosetting agent (f2) functions as a curing agent for the epoxy resin (f1).
Examples of the thermosetting agent (f2) include compounds having two or more functional groups capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is converted to an anhydride. It is preferably a phenolic hydroxyl group or an amino group.
The thermosetting agent (f2) may be used alone or in combination of two or more.

Among the thermal curing agents (f2), examples of the phenolic curing agent having a phenolic hydroxyl group include a polyfunctional phenol resin, biphenol, a novolak phenol resin, a dicyclopentadiene phenol resin, and an aralkyl phenol resin.
Among the thermosetting agents (f2), examples of the amine-based curing agent having an amino group include dicyandiamide.
The content of the thermosetting agent (f2) is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the epoxy resin (f1).

The content of the thermosetting component (f) (for example, the total content of the epoxy resin (f1) and the thermosetting agent (f2)) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b). Department.

[Curing accelerator (g)]
The curing accelerator (g) is a component for adjusting the curing speed of the energy ray-curable resin layer (I).
Preferred curing accelerators (g) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole , 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, imidazoles such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine, etc. Organic phosphines; and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.
When the curing accelerator (g) is used, the content of the curing accelerator (g) is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the thermosetting component (f).

[General purpose additive (z)]
The general-purpose additive (z) may be a known one and can be arbitrarily selected according to the purpose, and is not particularly limited. Examples thereof include a filler, a coloring agent, a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. And the like.
The general-purpose additive (z) may be used alone or in combination of two or more.

Examples of the filler include an inorganic filler and an organic filler, and by using these, the thermal expansion coefficient of the cured resin layer (I ′) can be adjusted.
The energy ray-curable resin layer (I) may or may not contain a filler, but if it contains a filler, its content can more effectively reduce the occurrence of warpage. From the viewpoint of suppression, it is preferably 5 to 87% by mass relative to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , More preferably 7 to 78% by mass.
Examples of the filler include those made of a heat conductive material.
Examples of the inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc .; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers Single crystal fibers of these inorganic fillers; glass fibers and the like.
The average particle size of the filler is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and still more preferably 0.3 to 10 μm. When the average particle diameter of the filler is in the above range, a decrease in the transmittance of the energy ray-curable resin layer (I) can be suppressed while maintaining the adhesiveness of the cured resin layer (I ′).

The energy ray-curable resin composition may or may not contain a coloring agent, but when the coloring agent is contained, the content is preferably as small as possible, and specifically, The amount is preferably less than 5% by mass, more preferably 0%, based on the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). 0.1 mass%, more preferably less than 0.01 mass%, even more preferably less than 0.001 mass%.

<< Production method of energy ray-curable resin composition >>
The energy ray-curable resin composition is obtained by blending each component for constituting the composition.
The order of addition of each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent may be mixed with any of the components other than the solvent to dilute the components in advance, or any of the components other than the solvent may be diluted in advance. Alternatively, a solvent may be used by mixing with these components.
The method of mixing each component at the time of compounding is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; What is necessary is just to select suitably.
The temperature and time during addition and mixing of each component are not particularly limited as long as each component is not deteriorated, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ° C.

Examples of the solvent include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; esters such as ethyl acetate; And amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. Among these, methyl ethyl ketone, toluene, and ethyl acetate are preferable in that the components contained in the energy ray-curable resin composition can be more uniformly mixed. The solvents may be used alone or in combination of two or more.

The energy ray-curable resin layer (I) may have a single-layer configuration or a configuration including two or more layers.
Examples of the energy ray-curable resin layer (I) composed of two or more layers include, for example, an energy ray-curable resin layer (I-) for providing a cured resin layer (I ′) having a high storage elastic modulus E ′. i) and an energy ray-curable resin layer (I-ii) having a high adhesive strength. In the case of having such a configuration, by disposing the energy ray-curable resin layer (I-ii) on the surface on which the object to be sealed is placed, the object to be sealed can be firmly fixed and After the curing, the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (Ii) effectively suppresses the warpage. Performance can be more highly compatible. The preferred composition and physical properties of the energy ray-curable resin layers (Ii) and (I-ii) depend on the desired function from the above-described preferred composition and physical properties of the energy ray-curable resin layer (I). What is necessary is just to select suitably and apply.

The thickness of the energy ray-curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, further preferably 10 to 200 μm, still more preferably 15 to 100 μm, and still more preferably 20 to 50 μm. is there. When the thickness of the energy ray-curable resin layer (I) is equal to or more than the lower limit, a cured sealing body in which warpage is more effectively suppressed can be obtained. , And excellent curability can be obtained.
Here, the “thickness of the energy-ray-curable resin layer (I)” means the entire thickness of the energy-ray-curable resin layer (I), for example, two or more energy-ray-curable resin layers. The thickness of (I) means the total thickness of all the layers constituting the energy ray-curable resin layer (I).

At 23 ° C., the storage elastic modulus E ′ of the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) is such that the curl is suppressed and warpage is suppressed with the cured resin layer having a flat surface. From the viewpoint of obtaining a laminated body from which the stopper can be manufactured, preferably, it is 1.0 × 10 ⁷ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more, still more preferably 5.0 × 10 ⁸ Pa or more, and still more. It is preferably 1.0 × 10 ⁹ or more, more preferably 1.0 × 10 ¹³ Pa or less, more preferably 1.0 × 10 ¹² Pa or less, further more preferably 5.0 × 10 ¹¹ Pa or less. More preferably, it is 1.0 × 10 ¹¹ Pa or less.

The visible light (wavelength: 380 nm to 750 nm) transmittance of the energy ray-curable resin layer (I) is preferably 5% or more, more preferably 10% or more, further preferably 30% or more, and still more preferably 50% or more. It is. When the visible light transmittance is in the above range, sufficient energy ray curability can be obtained. The upper limit of the visible light transmittance is not limited, but may be, for example, 95% or less. The transmittance can be measured according to a known method using a spectrophotometer.

<Production method of laminate>
In the laminate of one embodiment of the present invention, for example, the pressure-sensitive adhesive layer (X), the base material (Y), and the energy ray-curable resin layer (I) are separately formed so that these have a desired configuration. It can be manufactured by laminating. Each layer can be formed, for example, by applying and drying a resin composition for forming each layer on a release material.
However, the manufacturing method of the laminate of one embodiment of the present invention is not limited to the above method. For example, the base material (Y) is formed on the pressure-sensitive adhesive layer (X) formed on the release material. A method in which a resin composition (y) to be formed is applied, and then a resin composition is sequentially applied on a specific layer as in a method of applying an energy-ray-curable resin composition thereon. It may be a method of forming and multi-layering. At that time, a plurality of layers may be simultaneously applied using, for example, a multilayer coater or the like.

[Production method of cured sealing body]
A method for manufacturing a cured sealing body according to one embodiment of the present invention is a method for manufacturing a cured sealing body using the laminate according to one embodiment of the present invention, and includes the following steps (i) to (iv).
Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate. Step (ii): Applying the energy ray-curable resin layer (I). Step (iii) of irradiating an energy ray to form a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I): the sealing object and the sealing object At least the surface of the cured resin layer (I ′) at the peripheral portion is covered with a thermosetting sealing material, and the sealing material is thermoset to form a cured sealing body including the object to be sealed. Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by the treatment for expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer. Step Note that the cured sealing body in one embodiment of the present invention is obtained by covering an object to be sealed with a sealing material and curing the sealing material. There, composed of a cured product of the sealing object and the sealing material.

FIG. 4 is a schematic cross-sectional view showing a step of manufacturing a cured sealing body using the laminate 1a shown in FIG. Hereinafter, the respective steps described above will be described with reference to FIG.

<Step (i)>
Step (i) is a step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) included in the laminate of one embodiment of the present invention.
In FIG. 4A, in this step, the adhesive surface of the adhesive layer (X) of the support layer (II) is attached to the support 50 using the laminate 1a, and the energy ray-curable resin layer ( A state in which the sealing target 60 is placed on a part of the surface of (I) is shown.
Note that FIG. 4A illustrates an example in which the stacked body 1a illustrated in FIG. 1A is used; Then, a support, a laminate, and an object to be sealed are laminated or placed in this order.

The temperature condition in the step (i) is preferably performed at a temperature at which the thermally expandable particles do not expand, for example, in an environment of 0 to 80 ° C (provided that the expansion start temperature (t) is 60 to 80 ° C). In this case, it is preferable that the heat treatment be performed under an environment lower than the expansion start temperature (t).

The support is preferably attached to the entire surface of the adhesive surface of the adhesive layer (X) of the laminate.
Therefore, the support is preferably plate-shaped. Further, as shown in FIG. 4, the area of the surface of the support on the side to be adhered to the adhesive surface of the adhesive layer (X) is preferably equal to or larger than the area of the adhesive surface of the adhesive layer (X).

The material constituting the support is appropriately determined in consideration of the required properties such as mechanical strength and heat resistance according to the type of the object to be sealed, the type of the sealing material used in step (ii), and the like. Selected.
Specific examples of the material constituting the support include: metal materials such as SUS; nonmetallic inorganic materials such as glass and silicon wafer; epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic, polyimide resin, Resin materials such as polyamideimide resin; composite materials such as glass epoxy resin; and the like, among which SUS, glass, and silicon wafer are preferable. The support is preferably made of a transparent material such as glass from the viewpoint that the energy ray-curable resin layer (I) can be irradiated with energy rays through the support.
The engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like.
Examples of the super engineering plastic include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).

The thickness of the support is appropriately selected according to the type of the object to be sealed, the type of the sealing material used in step (ii), and the like, but is preferably 20 μm or more and 50 mm or less, more preferably 60 μm or more. It is 20 mm or less.

On the other hand, as a sealing target placed on a part of the surface of the energy ray-curable resin layer (I), for example, a semiconductor chip, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, And a substrate for a panel.

When the object to be sealed is a semiconductor chip, a semiconductor chip with a cured resin layer can be manufactured by using the laminate of one embodiment of the present invention.
A conventionally known semiconductor chip can be used, and an integrated circuit including a circuit element such as a transistor, a resistor, and a capacitor is formed on a circuit surface thereof.
The semiconductor chip is preferably mounted so that the back surface opposite to the circuit surface is covered with the surface of the energy ray-curable resin layer (I). In this case, after mounting, the circuit surface of the semiconductor chip is exposed.
For mounting the semiconductor chip, a known device such as a flip chip bonder or a die bonder can be used.
The layout and the number of semiconductor chips to be arranged may be determined as appropriate according to the form of the target package, the number of products to be produced, and the like.

Here, the laminated body of one embodiment of the present invention covers a semiconductor chip with a region larger than the chip size with a sealing material, such as FOWLP, FOPLP, or the like. It is preferable that the present invention is applied to a package in which a redistribution layer is formed even in the surface region of FIG.
Therefore, the semiconductor chip is mounted on a part of the surface of the energy ray-curable resin layer (I), and a plurality of semiconductor chips are arranged on the surface in a state where they are arranged at regular intervals. It is preferable that the semiconductor chips are mounted, and it is more preferable that the plurality of semiconductor chips are mounted on the surface in a state of being arranged in a matrix of a plurality of rows and a plurality of columns at a predetermined interval.
The distance between the semiconductor chips may be determined as appropriate depending on the desired package configuration and the like.

<Step (ii)>
Step (ii) is a step of irradiating the energy ray-curable resin layer (I) with energy rays to form a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I). is there.
FIG. 4B shows a state where the energy ray-curable resin layer (I) is cured in this step to form a cured resin layer (I ′).
The kind and irradiation condition of the energy ray are not particularly limited as long as the kind and condition are such that the energy ray-curable resin layer (I) is sufficiently cured to exhibit its function. What is necessary is just to select suitably according to the process which performs.
The illuminance of the energy beam during curing of the energy ray-curable resin layer (I) is preferably from 4 to 280 mW / cm ² , and the amount of energy beam during the curing is preferably from 5 to 1000 mJ / cm ^2. It is more preferably 100 to 500 mJ / cm ² .
The type of the energy beam and the irradiation device are as described above.
The energy ray may be irradiated from any direction as long as the energy ray can be irradiated to the energy ray-curable resin layer (I). For example, the support (II) and the support 50 may have a light transmittance By using a material excellent in the above, the light enters through the support (II) and the support 50 (that is, from the surface of the support 50 in FIG. 4B from the side opposite to the adhesive layer (X), The energy ray can be irradiated to the energy ray-curable resin layer (I) and the support 50, the pressure-sensitive adhesive layer (X) and the base material (Y).

<Step (iii)>
In the step (iii), the object to be sealed and the surface of the cured resin layer (I ′) at least at the peripheral portion of the object to be sealed are covered with a thermosetting sealing material (hereinafter referred to as “coating treatment”). This is a step of thermally curing the sealing material to form a cured sealing body including the object to be sealed.
In the covering process, first, the object to be sealed and at least the peripheral portion of the object to be sealed on the surface of the cured resin layer (I ′) are covered with a sealing material.
The sealing material covers the entire exposed surface of the object to be sealed and also fills the gap between the plurality of semiconductor chips.
For example, FIG. 4C shows a state in which the surface of the object 60 to be sealed and the surface of the cured resin layer (I ′) are entirely covered with the sealing material 70.

The sealing material has a function of protecting an object to be sealed and elements attached thereto from an external environment.
The sealing material used in the manufacturing method of one embodiment of the present invention is a thermosetting sealing material containing a thermosetting resin.
Further, the sealing material may be solid at room temperature, such as granules, pellets, and films, or may be a liquid in the form of a composition. Is preferred.

As the coating method, it is possible to appropriately select and apply the coating method according to the type of the sealing material from the methods applied to the conventional sealing step. For example, a roll lamination method, a vacuum press method, a vacuum lamination method Method, spin coating method, die coating method, transfer molding method, compression molding method and the like can be applied.

After performing the coating process, the sealing material is thermally cured to obtain a cured sealing body in which the object to be sealed is sealed with the sealing material.
Note that the thermosetting treatment in the step (iii) is performed at a temperature at which the thermally expandable particles do not expand. It is preferable that the heat treatment be performed under a temperature condition lower than the temperature (t).

In the manufacturing method of one embodiment of the present invention, as shown in FIG. 4C, the cured resin layer (I ′) is provided on the surface on the sealing object 60 side sealed with the sealing material 70. In the state, a thermosetting treatment is performed.
Since the cured resin layer (I ′) is provided, the difference in shrinkage stress between the two surfaces of the obtained cured sealing body can be reduced, and the warpage generated in the cured sealing body can be effectively suppressed. Conceivable.

<Step (iv)>
In the step (iv), the cured resin layer (I ′) and the support layer (II) are separated at the interface by the treatment for expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer. It is a process.
FIG. 4D shows a state where the heat-expandable particles are separated at the interface P between the cured resin layer (I ′) and the support layer (II) by a process of expanding the particles.
As shown in FIG. 4D, by separating at the interface P, a cured resin layer (I ′) having a cured sealing body 80 in which the sealing target 60 is sealed and a cured resin layer (I ′) is provided. The cured sealing body 100 can be obtained.
In addition, the presence of the cured resin layer (I ') has a function of effectively suppressing the warpage generated in the cured sealing body, protects the sealing object, and improves the reliability of the sealing object. Contribute.

The “expansion treatment” in the step (iv) is a treatment for expanding the heat-expandable particles by heating at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles, and the cured resin layer (I Unevenness occurs on the surface of the support layer (II) on the ') side. As a result, it is possible to easily separate the interface P at once with a small force.
The “temperature not lower than the expansion start temperature (t)” when expanding the thermally expandable particles is preferably “expansion start temperature (t) + 10 ° C.” or more and “expansion start temperature (t) + 60 ° C.” or less. It is more preferable that the temperature is not less than “expansion start temperature (t) + 15 ° C.” and not more than “expansion start temperature (t) + 40 ° C.”.
The heating method is not particularly limited, and examples thereof include a heating method using a hot plate, an oven, a baking furnace, an infrared lamp, a hot air blower, and the like. From the viewpoint of facilitating separation at the interface P, a method in which a heat source during heating can be provided on the support 50 side is preferable.

硬化 The cured sealing body with the cured resin layer thus obtained is further subjected to necessary processing thereafter. One example is described below. In the following description, an embodiment in which the semiconductor chip 60 is used as the sealing target 60 will be described.

<First grinding process>
FIG. 5A shows the cured resin body 100 with the cured resin layer obtained by the above-described manufacturing method, and FIG. A first grinding step is shown in which the surface 100a on the opposite side is ground by the grinding means 110 to expose the circuit surface 60a of the semiconductor chip 60.
The grinding means 110 is not particularly limited, and may be performed using a known grinding device such as a grinder.
When the first grinding step is performed, the surface of the cured sealing body on the cured resin layer (I ′) side is preferably fixed on another support from the viewpoint of workability.
Further, from the viewpoint of workability, dicing may be performed to a predetermined size including one or a plurality of chips before the first grinding step.

<Re-wiring layer and external terminal electrode forming step>
FIG. 5C illustrates a process of forming a rewiring layer 200 and an external terminal electrode 300 that are electrically connected to the circuit surface 60 a of the semiconductor chip 60 exposed on the surface of the cured sealing body 80 by the first grinding process. A wiring layer and an external terminal electrode forming step are shown.
The material of the redistribution layer 200 is not limited as long as it is a conductive material, and examples thereof include metals such as gold, silver, copper, and aluminum, and alloys containing these metals. The redistribution layer 200 can be formed by a known method such as a subtractive method or a semi-additive method. If necessary, one or more insulating layers may be provided.
The external terminal electrode 300 is electrically connected to an external electrode pad of the redistribution layer 200. The external electronic electrode 300 can be formed, for example, by soldering a solder ball or the like.

<Dicing process>
FIG. 5D shows a step of dicing the cured sealing body 100 with the cured resin layer to which the external terminal electrodes 300 are connected.
Dicing may be performed for each semiconductor chip, or may be performed for a predetermined size including a plurality of semiconductor chips. The method for dicing the cured sealing body 100 with the cured resin layer is not particularly limited, and can be implemented by a cutting means such as a dicing saw.

<Second grinding process>
FIG. 5E shows a second grinding step of grinding the cured resin layer (I ′) disposed on the side of the cured sealing body 80 opposite to the rewiring layer 200 by the grinding means 110. ing. At this time, the surface of the cured sealing body 80 on the rewiring layer 200 side is preferably fixed with a back grinding tape or the like. The grinding means 110 includes the same means as in the first grinding step.
In the second grinding step, a part of the cured resin layer (I ′) may be ground, or the entire cured resin layer (I ′) may be ground.
By grinding the cured resin layer (I ′), the size of the obtained semiconductor package can be further reduced. Therefore, from this viewpoint, it is preferable to grind the entire cured resin layer (I ′).
On the other hand, when the second grinding step is not performed or when only a part of the cured resin layer (I ′) is ground, the cured resin layer (I ′) also serves to protect the back surface of the semiconductor chip 60. be able to.

The present embodiment will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.
In the following description, the curable resin layer (I) means both the “energy beam curable resin layer (I)” and the “thermosetting resin layer”.
The physical property values in each example are values measured by the following methods.

<Mass average molecular weight (Mw)>
Using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name "HLC-8020"), the measurement was carried out under the following conditions, and the value measured in terms of standard polystyrene was used.
(Measurement condition)
-Column: TSK guard column HXL-L, TSK gel G2500HXL, TSK gel G2000HXL, TSK gel G1000HXL (all manufactured by Tosoh Corporation)-Column temperature: 40 ° C
・ Developing solvent: tetrahydrofuran ・ Flow rate: 1.0 mL / min

<Measurement of thickness of each layer>
The thickness was measured using a constant pressure thickness measuring instrument (model number: “PG-02J”, standard: JIS K6783, Z 1702, Z 1709) manufactured by Teclock Corporation.

<Methods for measuring expansion start temperature (t) and maximum expansion temperature of thermally expandable particles>
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 (5.65 mm inner diameter) and a depth of 4.8 mm, 0.5 mg of the thermally expandable particles to be measured are added, and an aluminum lid (5.6 mm in diameter, thickness of 0. 1 mm) is prepared.
Using a dynamic viscoelasticity measuring apparatus, the height of the sample is measured from the upper part of the aluminum lid while a force of 0.01 N is applied to the sample by a pressurizer. Then, with the force of 0.01 N applied by the pressurizer, the heater is heated from 20 ° C. to 300 ° C. at a rate of 10 ° C./min, and the displacement of the pressurizer in the vertical direction is measured. Let the displacement start temperature be the expansion start temperature (t).
The maximum expansion temperature was defined as the temperature at which the amount of displacement measured by the above method became maximum.

<Evaluation of warpage>
The curable resin layer (I) of the sheet for forming the curable resin layer (I) produced in each example was attached to a silicon wafer (size: 12 inches, thickness: 100 μm).
Next, as a thermosetting resin composition, a resin composition obtained by mixing an epoxy resin (manufactured by Struers, product name “Epofix resin”) and a curing agent (manufactured by Struers, product name “Epofix hardener”) A product was prepared, and the resin composition was applied to the surface of the silicon wafer on the side opposite to the curable resin layer (I) so as to have a thickness of 30 μm. As a result, a measurement sample before curing having the curable resin layer (I) / the silicon wafer / the thermosetting resin composition layer in this order was obtained.
Subsequently, when the curable resin layer (I) is the energy ray-curable resin layer (I), the ultraviolet rays are irradiated with an irradiance of 215 mW / cm ² using an ultraviolet irradiation apparatus RAD-2000 (manufactured by Lintec Corporation). Irradiation was performed three times under the condition of a light amount of 187 mJ / cm ² to cure the energy ray-curable resin layer (I) to form a cured resin layer (I ′). When the curable resin layer (I) was a thermosetting resin layer (I), it was cured by heating at 180 ° C. for 60 minutes to form a cured resin layer (I ′). Thereafter, the thermosetting resin composition is heated and cured to form a thermosetting resin layer, and a cured measurement sample having a cured resin layer (I ′) / silicon wafer / thermosetting resin layer in this order is prepared. Obtained.
After the cured sample was placed on a horizontal table, it was visually observed, and the presence or absence of warpage was evaluated based on the following criteria. The “silicon wafer / thermosetting resin layer” portion in the measurement sample after curing has a configuration corresponding to a cured sealing body obtained by sealing a semiconductor chip with a thermosetting resin. The performance of the layer (I ′) as a warp prevention layer can be evaluated.
A: The amount of warpage is 3 mm or less.
B: The amount of warpage is larger than 3 mm and smaller than 15 mm.
C: The amount of warpage is 15 mm or more.
In addition, when the silicon wafer / thermosetting resin layer was formed in the same procedure as above without attaching the curable resin layer (I), the amount of warpage was 15 mm.

<Evaluation of separability>
After attaching a silicon wafer to the surface of the curable resin layer (I) of the laminate obtained in each example, the curable resin layer (I) is cured by energy rays or heat to form a cured resin layer (I '). Was formed. Next, the expandable base material layer (Y1) is expanded by a heat expansion treatment to separate the cured resin layer (I ′) and the support layer (II), and the separation property is evaluated based on the following criteria. did. The curing conditions for the curable resin layer (I) and the thermal expansion treatment for the support layer (II) manufactured in each example were the same as those described in Examples 1 to 5 and Reference Example 1 described later. .
A: Separable, the appearance of the cured resin layer (I ') is good, and there is no adhesive residue.
B: Separable, the appearance of the cured resin layer (I ') is good, but adhesive residue is partially present.
C: It cannot be separated, or there is adhesive residue on the entire surface of the cured resin layer (I ′), or the appearance of the cured resin layer (I ′) is poor.

<Storage modulus E ′ of intumescent base material layer (Y1)>
A 200 μm thick expandable base material layer (Y1) prepared for the measurement of the storage elastic modulus E ′ was 5 mm long × 30 mm wide × 200 μm thick, and a test sample was obtained by removing the release material.
Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments Co., Ltd., product name “DMAQ800”), the test start temperature is 0 ° C., the test end temperature is 300 ° C., the heating rate is 3 ° C./min, the frequency is 1 Hz, and the amplitude is 20 μm. The storage elastic modulus E ′ of the test sample at a predetermined temperature was measured under the following conditions.

<Storage Shear Modulus G ′ of First Adhesive Layer (X1) and Second Adhesive Layer (X2)>
The first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) were cut into a circle having a diameter of 8 mm, the release material was removed, and the resultant was superposed to form a test sample having a thickness of 3 mm. .
Using a viscoelasticity measuring device (manufactured by Anton Paar, device name "MCR300"), a torsional shear method under the conditions of a test start temperature of 0 ° C, a test end temperature of 300 ° C, a heating rate of 3 ° C / min, and a frequency of 1 Hz. The storage shear modulus G 'of the test sample at a predetermined temperature was measured.

<Storage elastic modulus E ′ of cured resin layer (I ′)>
Using a cured specimen of the curable resin layer (I) obtained in each example as a test piece, using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name “DMAQ800”), the test start temperature The storage elastic modulus E ′ of the formed cured resin layer (I ′) was measured at 23 ° C. under the conditions of 0 ° C., a test termination temperature of 300 ° C., a temperature rising rate of 3 ° C./min, a vibration frequency of 11 Hz, and an amplitude of 20 μm. When the curable resin layer (I) is the energy ray-curable resin layer (I), the test piece was irradiated with ultraviolet light by using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Corporation) at an illuminance of 215 mW. / Cm ² and a light amount of 187 mJ / cm ² , and cured by heating three times. If the curable resin layer (I) is a thermosetting resin layer (I), heat at 180 ° C. for 60 minutes. And cured.

Synthesis Example 1
(Synthesis of "acrylic urethane resin" used for intumescent base material layer (Y1))
In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate was added to 100 parts by mass of a polycarbonate diol (carbonate type diol) having a mass average molecular weight of 1,000, and the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of isophorone diisocyanate was 1 / L, further added 160 parts by mass of toluene, and reacted at 80 ° C for 6 hours or more with stirring under a nitrogen atmosphere until the isocyanate group concentration reached the theoretical amount.
Next, a solution obtained by diluting 1.44 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added, and the mixture was further reacted at 80 ° C. for 6 hours until the isocyanate groups at both ends disappeared. A urethane prepolymer having an average molecular weight of 29,000 was obtained.
Subsequently, 100 parts by mass of the urethane prepolymer obtained above, 117 parts by mass of methyl methacrylate (MMA), 5.1 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) were placed in a reaction vessel under a nitrogen atmosphere. 1.1 parts by mass of thioglycerol and 50 parts by mass of toluene were added, and the mixture was heated to 105 ° C. with stirring. Then, a solution prepared by diluting 2.2 parts by mass of a radical initiator (manufactured by Nippon Finechem Co., Ltd., product name “ABN-E”) with 210 parts by mass of toluene was further added to the reaction vessel for 4 hours while maintaining the temperature at 105 ° C. It dripped over.
After the completion of the dropwise addition, the mixture was reacted at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin having a weight average molecular weight of 105,000.

[Production of sheet for forming support layer (II)]
Production Example 1
(Support layer (II-A))
A support layer (II-A) forming sheet was prepared according to the following procedures (1-1) to (1-4).
Details of the materials used for forming each layer are as follows.

<Adhesive resin>
Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio) An acrylic copolymer having a Mw of 600,000.
Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid = 86.0 / 8.0 / 5.0 / 1. An acrylic copolymer having a Mw of 600,000 and having a structural unit derived from a raw material monomer having a mass ratio of 0 (mass ratio).
<Additives>
-Isocyanate crosslinking agent (i): manufactured by Tosoh Corporation, product name "Coronate L", solid content concentration: 75% by mass.
<Thermal expandable particles>
- heat-expandable particles A: manufactured by Kureha Corporation, product name "S2640", expansion starting temperature (t) = 208 ℃, the average particle diameter _{(D 50) = 24μm, 90} % particle diameter _(D 90) = _49μm.
<Release material>
-Heavy release film: manufactured by Lintec Co., Ltd., product name "SP-PET382150", a polyethylene terephthalate (PET) film provided with a release agent layer formed of a silicone release agent on one surface, thickness: 38 µm.
-Light release film: manufactured by Lintec Co., Ltd., product name "SP-PET381031", a PET film provided with a release agent layer formed of a silicone release agent on one side of the PET film, thickness: 38 µm.

(1-1) Formation of First Pressure-Sensitive Adhesive Layer (X1) 5.0 parts by mass of the isocyanate-based crosslinking agent (i) was added to 100 parts by mass of the solid content of the acrylic copolymer (i) as an adhesive resin. Parts were mixed, diluted with toluene, and uniformly stirred to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass.
Then, the pressure-sensitive adhesive composition is applied to a surface of the release agent layer of the heavy release film (hereinafter, also referred to as a “release treated surface”) to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds. Thus, a first pressure-sensitive adhesive layer (X1), which was a non-thermally-expandable pressure-sensitive adhesive layer having a thickness of 5 μm, was formed.
In addition, the storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X1) at 23 ° C. was 2.5 × 10 ⁵ Pa.
Further, the adhesion at 23 ° C. of the first pressure-sensitive adhesive layer (X1) measured based on the above method was 0.3 N / 25 mm.

(1-2) Formation of the second pressure-sensitive adhesive layer (X2) 0.8 mass of the isocyanate-based crosslinking agent (i) is added to 100 mass parts of the solid content of the acrylic copolymer (ii), which is a pressure-sensitive resin. Parts were mixed, diluted with toluene, and uniformly stirred to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass.
Then, the pressure-sensitive adhesive composition is applied to the release-treated surface of the light release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to form a second pressure-sensitive adhesive layer having a thickness of 10 μm ( X2).
At 23 ° C., the storage shear modulus G ′ (23) of the second pressure-sensitive adhesive layer (X2) was 9.0 × 10 ⁴ Pa.
Further, the adhesion at 23 ° C. of the second pressure-sensitive adhesive layer (X2) measured according to the above method was 1.0 N / 25 mm.

(1-3) Preparation of Base Material (Y) To 100 parts by mass of the solid content of the acrylic urethane-based resin obtained in Synthesis Example 1, 6.3 parts by mass of the isocyanate-based crosslinking agent (i), and dioctyltin bis as a catalyst 1.4 parts by mass of (2-ethylhexanoate) and the above-mentioned heat-expandable particles A were mixed, diluted with toluene, and uniformly stirred to obtain a resin composition having a solid content concentration (active ingredient concentration) of 30% by mass. Was prepared.
The content of the thermally expandable particles A was 20% by mass relative to the total amount (100% by mass) of the active ingredients in the obtained resin composition.
Then, on a surface of a non-expandable substrate, a 50 μm thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “Cosmoshine A4100”, probe tack value: 0 mN / 5 mmφ), the resin composition The product was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to form an intumescent base material layer (Y1) having a thickness of 50 μm.
Here, the PET film as the non-expandable base material corresponds to the non-expandable base material layer (Y2).
As described above, the base material (Y) including the 50 μm-thick expandable base material layer (Y1) and the 50 μm-thick non-expandable base material layer (Y2) was produced.

As a sample for measuring the storage elastic modulus E ′ and the probe tack value of the expandable base material layer (Y1), the resin composition was applied to the release-treated surface of the light release film to form a coating film, The coating film was dried at an ambient temperature of 100 ° C. for 120 seconds to form a 200 μm thick expandable base material layer (Y1) in the same manner.
Then, based on the above-described measurement method, the storage elastic modulus and the probe tack value at each temperature of the expandable base material layer (Y1) were measured. The measurement results were as follows.
-Storage elastic modulus E '(23) at 23 ° C = 2.0 x 10 ⁸ Pa
-Storage elastic modulus E '(100) at 100 ° C = 3.0 × 10 ⁶ Pa
-Storage elastic modulus at 208 ° C E '(208) = 5.0 x 10 ⁵ Pa
・ Probe tack value = 0mN / 5mmφ

(1-4) Lamination of Each Layer The non-expandable base material layer (Y2) of the base material (Y) prepared in the above (1-3) and the second pressure-sensitive adhesive layer (X2 ), And the expandable base material layer (Y1) and the first pressure-sensitive adhesive layer (X1) formed in (1-1) above were bonded.
Then, the light release film / second pressure-sensitive adhesive layer (X2) / non-expandable base material layer (Y2) / expandable base material layer (Y1) / first pressure-sensitive adhesive layer (X1) / heavy release film in this order. A laminated sheet for forming a support layer (II-A) was prepared.

Production Example 2
(Supporting layer (II-B))
In Production Example 1, the heat-expandable particles A were changed to the following heat-expandable particles B, and the drying conditions after applying the resin composition to form a coating film were changed to an atmosphere temperature of 100 ° C. for 1 minute. Except for this, in the same manner as in Production Example 1, a sheet for forming a support layer (II-B) was produced.
Thermal expansion particles B: manufactured by Nippon Philite Co., Ltd., product name “031-40DU”, expansion start temperature (t) = 80 ° C.

Production Example 3
(Support layer (II-C))
In Production Example 1, the heat-expandable particles A were changed to the following heat-expandable particles C, and the drying conditions after applying the resin composition to form a coating film were changed to an atmosphere temperature of 100 ° C. for 1 minute. Except for this, in the same manner as in Production Example 1, a sheet for forming a support layer (II-C) was produced.
Thermal expansion particles C: manufactured by Nippon Philite Co., Ltd., product name “053-40DU”, expansion start temperature (t) = 100 ° C.

In Production Examples 2 and 3, when forming the support layer (II) -forming sheet, the drying temperature after applying the resin composition to form a coating film is set to the expansion starting temperature of the thermally expandable particles ( Although it was higher than t), no foaming was observed in the formed support layer (II) because the drying temperature was the ambient temperature.

Production Example 4
(Support layer (II-D))
In Production Example 1, the heat-expandable particles A were changed to the following heat-expandable particles D, and the drying conditions after applying the resin composition to form a coating film were changed to an atmosphere temperature of 100 ° C. for 1 minute. Except for this, in the same manner as in Production Example 1, a sheet for forming a support layer (II-D) was produced.
Thermal expansion particles D: manufactured by Nippon Philite Co., Ltd., product name “920-40DU”, expansion start temperature (t) = 120 ° C.

[Production of sheet for forming curable resin layer (I)]
Production Example 5
(Energy ray-curable resin layer (IA))
A curable composition having a solid content (active ingredient concentration) of 61% by mass was prepared by blending the components of the types and amounts shown below (all of which are "active ingredient ratios"), further diluting with methyl ethyl ketone, and stirring uniformly. Was prepared.
[Component (a2)]
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name “KAYARAD DPHA”): 17.6 parts by mass [component (b)]
Acrylic polymer: butyl acrylate (BA) (55 parts by mass), methyl acrylate (MA) (10 parts by mass), glycidyl methacrylate (GMA) (20 parts by mass), and 2-hydroxyethyl acrylate ( Acrylic resin obtained by copolymerizing (HEA) (15 parts by mass) (glass transition temperature: -28 ° C., Mw: 800,000): 17 parts by mass [component (c)]
-Phenyl 1-hydroxycyclohexyl ketone (product name "IRGACURE-184" manufactured by BASF): 0.5 parts by mass [component (d)]
-Epoxy group-containing oligomeric silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"): 0.6 parts by mass [component (e)]
・ TDI-based crosslinking agent (Toyochem Corporation, product name “BHS-8515”): 0.5 parts by mass [component (f)]
-Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name "BPA328"): 16 parts by mass-Dicyclopentadiene type epoxy resin (Nippon Shokubai Co., Ltd., product name "XD-1000L"): 18 parts by mass・ Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, product name “HP-7200HH”): 27 parts by mass ・ Dicyandiamide (manufactured by ADEKA Corporation, product name “Adecover donor 3636AS”): 1.5 parts by mass [( g) component]
・ Imidazole (manufactured by Shikoku Chemicals Co., Ltd., product name “2PH-Z”): 1.5 parts by mass

The solution of the curable composition prepared above was applied on the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes, and the energy beam having a thickness of 25 μm was obtained. The curable resin layer (IA) was formed, and a sheet for forming the energy ray-curable resin layer (IA) composed of the energy ray-curable resin layer (IA) and the light release film was prepared.

Production Example 6
(Energy ray-curable resin layer (IB))
A curable composition having a solid content (active ingredient concentration) of 61% by mass was prepared by blending the components of the types and amounts shown below (all of which are "active ingredient ratios"), further diluting with methyl ethyl ketone, and stirring uniformly. Was prepared.
[Component (a2)]
Ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name “A-9300-1CL”, trifunctional ultraviolet curable compound): 10 parts by mass [(b) component]
Acrylic resin: Acrylic resin obtained by copolymerizing methyl acrylate (MA) (85 parts by mass) / 2-hydroxyethyl acrylate (HEA) (15 parts by mass): 28 parts by mass [component (c) ]
-2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (manufactured by BASF, product name "Irgacure (registered trademark) 369"): 0.6 parts by mass [(d) component]
・ 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name “KBM-503”): 0.4 parts by mass [component (h)]
・ Silica filler (fused quartz filler, average particle size 8 μm): 57 parts by mass [(z) component]
32 parts by mass of a phthalocyanine-based blue pigment (Pigment Blue 15: 3), 18 parts by mass of an isoindolinone-based yellow pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone-based red pigment (Pigment Red 177), Pigment obtained by pigmenting so that the total amount of the above three dyes / the amount of styrene acrylic resin = 1/3 (mass ratio): 4 parts by mass

The solution of the curable composition prepared above was applied on the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes, and the energy beam having a thickness of 25 μm was obtained. The curable resin layer (IB) was formed, and a sheet for forming the energy ray-curable resin layer (IB) including the energy ray-curable resin layer (IB) and the light release film was prepared.

Production Example 7
(Thermosetting resin layer (IC))
The following types and amounts (all of which are "active ingredient ratios") are blended, diluted with methyl ethyl ketone, and uniformly stirred to obtain a solid concentration (active ingredient concentration) of 61% by mass. A solution of the acidic composition was prepared.
Acrylic polymer: butyl acrylate (BA) (1 part by mass), methyl acrylate (MA) (74 parts by mass), glycidyl methacrylate (GMA) (15 parts by mass) and 2-hydroxyethyl acrylate ( HEA) (10 parts by mass) acrylic resin (glass transition temperature: 8 ° C., Mw: 440,000): 18 parts by mass liquid bisphenol A type epoxy resin (product name: Nippon Shokubai Co., Ltd.) BPA328 "): 3 parts by mass, solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name" Epicoat 1055 "): 20 parts by mass, dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name" XD-1000L "): 1.5 parts by mass dicyandiamide (ADEKA Corp., product name" Adecover donor 3636AS "): 0.5 quality Part: imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name "2PH-Z"): 0.5 parts by mass-epoxy group-containing oligomer type silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"): 0 0.5 parts by mass, spherical silica filler (manufactured by Admatechs Co., Ltd., product name "SC2050MA"): 6 parts by mass, spherical silica filler (Tatsumori Corporation, product name "SV-10"): 50 parts by mass

The above-prepared solution of the curable composition is applied on the release-treated surface of the light release film to form a coating film, and the coating film is dried at 120 ° C. for 2 minutes, and thermally cured to a thickness of 25 μm. The thermosetting resin layer (IC) was formed, and a thermosetting resin layer (IC) forming sheet composed of the thermosetting resin layer (IC) and the light release film was prepared.

[Production of laminated body]
Examples 1 to 5, Reference Example 1
The heavy release film of the support layer (II) forming sheet shown in Table 1 was removed and the exposed first pressure-sensitive adhesive layer (X1) and the curable resin layer (I) forming sheet shown in Table 1 were cured. The surface of the resin layer (I) was bonded to obtain a laminate. In Example 5, as the sheet for forming the support layer (II-E), a product name “Riba Alpha 3195” (expansion start temperature (t) = 170 ° C.) manufactured by Nitto Denko Corporation was used.
Table 1 shows the evaluation results of the separability and warpage of the laminate obtained in each example.

[Production of cured sealing body]
Subsequently, using the laminate obtained in each example, a cured sealing body was produced by the following procedure.

(1) Placement of Semiconductor Chip The light release film on the support layer (II) side of the laminate is removed, and the exposed adhesive surface of the second adhesive layer (X2) of the support layer (II) is exposed to the support ( (Glass).
Then, the light release film on the curable resin layer (I) side is also removed, and 9 semiconductor chips (each chip size is 6.4 mm × 6. 4 mm and a chip thickness of 200 μm (♯2000)) were mounted at necessary intervals so that the back surface opposite to the circuit surface of each semiconductor chip was in contact with the surface of the curable resin layer (I). .

(2) Formation of Cured Resin Layer (I ′) In Examples 1 to 5, after the above (1) and before the following (3), the energy ray curable resin layer which is the curable resin layer (I) Ultraviolet (UV) light was applied to (I) to form a cured resin layer (I ′) on which the semiconductor chip was mounted. The ultraviolet rays were irradiated three times from the support (glass) side using an ultraviolet irradiation apparatus RAD-2000 (manufactured by Lintec Corporation) under the conditions of illuminance of 215 mW / cm ² and light amount of 187 mJ / cm ² .
In Reference Example 1, the thermosetting resin layer, which is the curable resin layer (I), was simultaneously cured in the process of curing the sealing material in (3) described later without performing (2).

(3) Formation of a cured sealing body Nine semiconductor chips and the surface of the cured resin layer (I ′) (the thermosetting resin layer in Reference Example 1) at least at the peripheral portion of the semiconductor chip are sealed. The sealing resin film is covered with a thermosetting sealing resin film, which is a stopper material, and the sealing resin film is heat-cured using a vacuum heating / pressurizing laminator (product name: 7024HP5, manufactured by ROHM and HAAS) and cured and sealed. A stop body was produced. The sealing conditions are as follows.
・ Preheating temperature: 100 ° C for both table and diaphragm
・ Evacuation: 60 seconds ・ Dynamic press mode: 30 seconds ・ Static press mode: 10 seconds ・ Sealing temperature: 180 ° C. × 60 minutes

(4) Separation at Interface P After the above (3), heat expansion treatment is performed for 3 minutes at the temperature of the expansion start temperature (t) of the thermally expandable particles contained in the support layer (II) of each laminate + 30 ° C for 3 minutes. Was carried out to separate at the interface P between the first pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I ′). Thereby, a cured sealing body with a cured resin layer was obtained.

From Table 1, it is found that in Examples 1 to 5 using the laminated body which is one embodiment of the present invention, the formed cured body does not warp and has excellent separation of the support layer (II). Was.
On the other hand, in Reference Example 1 in which a thermosetting resin layer was used as the curable resin layer, the support layer (II) could not be separated from the cured resin layer (I ′).

1a, 1b, 2a, 2b, 3 laminate (I) Energy ray-curable resin layer (I ') Cured resin layer (II) Support layer (X) Adhesive layer (X1) First adhesive layer (X2) 2 Adhesive layer (Y) Base material (Y1) Expandable base material layer (Y2) Non-expandable base material layer 50 Support body 60 Object to be sealed (semiconductor chip)
Reference Signs List 70 sealing material 80 cured sealing body 100 cured sealing layer 100a with cured resin layer cured sealing body surface 110 grinding means 200 rewiring layer 300 external terminal electrode

Claims

Energy ray-curable resin layer (I),
A support layer (II) for supporting the energy ray-curable resin layer (I),
The energy ray-curable resin layer (I) has a surface having tackiness,
The support layer (II) has a substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles;
A laminate in which a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) and a support layer (II) are separated at an interface thereof by a process of expanding the thermally expandable particles.
The storage elastic modulus E ′ at 23 ° C. of the cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I) is 1.0 × 10 7 to 1.0 × 10 13 Pa. Item 7. The laminate according to Item 1.
The laminate according to claim 1, wherein the energy ray-curable resin layer (I) has a thickness of 1 to 500 μm.
The laminate according to any one of claims 1 to 3, wherein the visible ray transmittance of the energy ray-curable resin layer (I) is 5% or more.
(5) The laminate according to any one of (1) to (4), wherein the base material (Y) has an expandable base material layer (Y1) containing the thermally expandable particles.
The laminate according to claim 5, wherein the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer.
The laminate according to claim 5, wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.
The base material (Y) has a non-expandable base material layer (Y2) and an expansible base material layer (Y1),
The support layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X) in this order,
The laminate according to any one of claims 5 to 7, wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.
An object to be sealed is placed on a part of the surface of the energy ray-curable resin layer (I),
Irradiating the energy ray-curable resin layer (I) with energy rays to form a cured resin layer (I ′) obtained by curing the energy ray-curable resin layer (I),
The object to be sealed and the surface of the cured resin layer (I ') at least in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material,
After the sealing material is thermally cured, the cured resin layer (I ′) and the support layer (II) are separated at the interface by a process of expanding the thermally expandable particles, and the object to be sealed is removed. The laminate according to any one of claims 1 to 8, which is used for forming a cured sealing body containing the laminate.
The laminate according to claim 9, which is used to prevent the cured sealing body from warping.
A method for producing a cured encapsulant using the laminate according to any one of claims 1 to 10, wherein the method comprises the following steps (i) to (iv).
Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate. Step (ii): Applying the energy ray-curable resin layer (I). Step (iii) of forming a cured resin layer (I ′) obtained by irradiating an energy ray and curing the energy ray-curable resin layer (I): the sealing object and the sealing object At least the surface of the cured resin layer (I ′) at the peripheral portion is covered with a thermosetting sealing material, and the sealing material is thermoset to form a cured sealing body including the object to be sealed. Step (iv): The cured resin layer (I ′) and the support layer (II) are separated at the interface by the treatment for expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer. Process