JPWO2019131408A1 - A method for manufacturing an adhesive laminate, a processed object with a resin film, and a method for manufacturing a cured seal with a cured resin film. - Google Patents

Abstract

A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1) and containing heat-expandable particles in any of the layers, a base material (Y2) and a curable resin layer ( A resin film forming sheet (II) having Z2) is provided, and the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) are directly laminated to perform a predetermined process. An adhesive laminate used to fix an object to be processed to a support during application, and is a pressure-sensitive adhesive sheet (adhesive sheet) by heat treatment at a temperature equal to or higher than the thermal expansion start temperature (t) of the heat-expandable particles. An adhesive laminate that can be separated at the interface P between I) and the base material (Y2) of the resin film forming sheet (II) was prepared.

Description

The present invention relates to an adhesive laminate, a method for producing a processed object with a resin film using the adhesive laminate, and a method for producing a cured seal with a cured resin film.

Adhesive sheets are used not only for semi-permanently fixing members, but also for temporary fixing of target members when processing or inspecting building materials, interior materials, electronic parts, etc. May be done.
Such an adhesive sheet for temporary fixing is required to have both adhesiveness at the time of use and peelability after use.

For example, Patent Document 1 discloses a heat-release type pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material. ing.
This heat-release type pressure-sensitive adhesive sheet adjusts the maximum particle size of the heat-expandable microspheres with respect to the thickness of the heat-expandable pressure-sensitive adhesive layer, and adjusts the center line average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating. It is adjusted to 0.4 μm or less.
According to Patent Document 1, the heat-removable adhesive sheet can secure a contact area with an adherend when cutting an electronic component, so that it can exhibit adhesiveness capable of preventing adhesive defects such as chip skipping. There is a description that after use, the heat-expandable microspheres can be expanded by heating to reduce the contact area with the adherend, so that the microspheres can be easily peeled off.

Japanese Patent No. 3594853

In the process of processing using an adhesive sheet as described in Patent Document 1, an object to be processed using the adhesive sheet (hereinafter, also referred to as “processed object”) is temporarily fixed to the processed object. After performing the processing, the object to be processed is separated from the adhesive sheet.
By the way, especially in the manufacture of electronic parts, there are many cases where a plurality of processing steps are performed.
When a plurality of processing steps are required for the object to be processed, the object to be processed after the processing is separated from the adhesive sheet, attached to a new adhesive sheet again, and then processed in the next step. May be offered to.

However, the work of attaching the object to be processed to a new adhesive sheet for each process is complicated and leads to a decrease in product productivity.
For example, a cured resin is used to protect the back surface side of a processed object such as a semiconductor chip that has been attached to an adhesive sheet and have undergone a predetermined process, or to impart a die bonding function. A film may be formed. For this purpose, a resin film forming sheet having a curable resin layer may be used.
In this case, after separating the object to be processed from the adhesive sheet, a separately prepared resin film forming sheet having a curable resin layer is attached to the object to be processed and cured on the curable resin layer to cure the cured resin film. It is common to form.
That is, in order to obtain a processed object with a cured resin film, there are two methods, such as attaching an adhesive sheet for performing a predetermined process and a resin film forming sheet for forming the cured resin film. Pasting work was required.

According to the present invention, the object to be processed can be fixed to the support to perform a predetermined process, and after the process, the object to be processed can be easily separated from the support collectively with a slight force, and the support can be separated. It is an object of the present invention to provide an adhesive laminate capable of obtaining a processed object with a resin film by separating from the resin film.

The present inventors have a heat-expandable pressure-sensitive adhesive sheet (I) having a base material and a pressure-sensitive adhesive layer, and one of which contains a layer containing heat-expandable particles, and a base material and a curable resin layer. An adhesive laminate having the resin film-forming sheet (II) and the adhesive sheet (I) and the base material of the resin film-forming sheet (II) directly laminated can solve the above problems. I found.

That is, the present invention relates to the following [1] to [13].
[1] A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1) and containing heat-expandable particles in any of the layers.
A resin film forming sheet (II) having a base material (Y2) and a curable resin layer (Z2) is provided.
The adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) are directly laminated.
An adhesive laminate used to fix an object to be processed to a support when performing a predetermined process.
The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support.
The surface of the curable resin layer (Z2) of the resin film forming sheet (II) is a surface to which the object to be processed is attached.
By heat treatment at a temperature equal to or higher than the thermal expansion start temperature (t) of the thermally expandable particles, the adhesive sheet (I) can be separated at the interface P between the base material (Y2) of the resin film forming sheet (II). Is an adhesive laminate.
[2] The adhesive laminate according to the above [1], wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270 ° C.
[3] The adhesive according to the above [1] or [2], wherein the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) containing the heat-expandable particles. Sex laminate.
[4] In the above [3], the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2). The adhesive laminate according to the description.
[5] The heat-expandable base material layer (Y1-1) of the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated. , The adhesive laminate according to the above [3] or [4].
[6] The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12).
It has a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
The adhesive laminate according to any one of [3] to [5] above, wherein the surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface to be attached to the support.
[7] The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12).
The first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles.
The second pressure-sensitive adhesive layer (X12) is a non-thermally expandable pressure-sensitive adhesive layer.
It has a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
The adhesive laminate according to the above [1] or [2], wherein the surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface to be attached to the support.
[8] The adhesiveness according to any one of [1] to [7] above, wherein the surface on the side where the adhesive sheet (I) of the base material (Y2) is laminated is the surface to which the peeling treatment has been performed. Laminated body.
[9] The above-mentioned [1] to [8], wherein the curable resin layer (Z2) is a layer formed from a curable composition (z) containing a polymer component (A) and a curable component (B). The adhesive laminate according to any one of the above.
[10] A method for producing a processed object with a resin film using the adhesive laminate according to any one of the above [1] to [9].
A method for producing a processed object with a resin film, which comprises the following steps (α-1) to (α-3).
Step (α-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. Step / step (α-2) of placing or affixing the object to be processed on the surface of Z2): Step / step (α-3) of performing a predetermined process on the object to be processed: heat of the thermostable particles A step of separating the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) at the interface P by heating at the expansion start temperature (t) or higher to obtain a processed object with a resin film. [11] The method for producing a processed object with a resin film according to the above [10], wherein the curable resin layer (Z2) is cured to form a cured resin film in the step (α-2).
[12] The method for producing a processed object with a resin film according to the above [10], which comprises the following step (α-2') after the step (α-2) and before the step (α-3).
-Step (α-2'): A step of curing the curable resin layer (Z2) to form a cured resin film.
[13] A method for producing a cured encapsulant with a cured resin film using the adhesive laminate according to any one of the above [1] to [9].
A method for producing a cured encapsulant with a cured resin film, which comprises the following steps (β-1) to (β-3).
Step (β-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. Step / Step (β-2) of placing a semiconductor chip on Z2): The semiconductor chip is coated with a sealing material, the sealing material is cured, and the semiconductor chip is sealed. Step / Step (β-3) of curing the body and the curable resin layer (Z2) to form a curable resin film: Adhesion by heating the thermosetting particles at a thermal expansion start temperature (t) or higher. A step of separating the sheet (I) and the base material (Y2) of the resin film forming sheet (II) at the interface P to obtain a cured encapsulant with a cured resin film.

In the adhesive laminate of the present invention, the object to be processed can be fixed to the support to carry out a predetermined process, and after the process, the adhesive laminate can be easily separated from the support collectively with a slight force. Moreover, by separating from the support, a processed object with a resin film can be obtained.

It is sectional drawing of the adhesive laminate which shows the structure of the adhesive laminate of the 1st aspect of this invention. It is sectional drawing of the adhesive laminate which shows the structure of the adhesive laminate of the 2nd aspect of this invention. It is sectional drawing of the adhesive laminate which shows the structure of the adhesive laminate of the 3rd aspect of this invention. (A) is a schematic cross-sectional view showing an example of a state in which an object to be processed and inspected is fixed to a support via an adhesive laminate of the present invention, and (b) is separated at an interface P by heat treatment. It is sectional drawing which shows the state.

In the present specification, whether or not the target layer is a "non-thermally expandable layer" is determined as follows.
The target layer is heat-treated for 3 minutes at the expansion start temperature (t) of the heat-expandable particles contained in the layer containing the heat-expandable particles. When the volume change rate calculated from the following formula is less than 5%, it is determined that the layer is a "non-thermally expandable layer".
Volume change rate (%) = {(volume of the layer after heat treatment-volume of the layer before heat treatment) / volume of the layer before heat treatment} × 100

As used herein, the term "active ingredient" refers to a component contained in a target composition excluding a diluting solvent.
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. Is.
In the present specification, for example, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also used.
In the present specification, the lower limit value and the upper limit value described stepwise for a preferable numerical range (for example, a range such as content) can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". You can also do it.

[Structure of adhesive laminate]
The adhesive laminate of the present invention has a heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1), and the heat-expandable particles are contained in any of the layers, and a base material. A resin film forming sheet (II) having (Y2) and a curable resin layer (Z2) is provided, and the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) are directly connected to each other. It is laminated and is used to fix the object to be processed to the support when performing a predetermined process.

In the adhesive laminate of the present invention, the surface of the adhesive layer (X1) of the adhesive sheet (I) is the surface to be attached to the support.
That is, the pressure-sensitive adhesive sheet (I) has at least one pressure-sensitive adhesive layer (X1), and the surface of one pressure-sensitive adhesive layer (X1) is attached to the surface of the support.
When the pressure-sensitive adhesive sheet (I) has the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) on both sides of the base material (Y1), the surface of the second pressure-sensitive adhesive layer (X12) is It is a surface to be attached to the support, and the surface of the first pressure-sensitive adhesive layer (X11) is a surface to be attached to the base material (Y2) of the resin film forming sheet (II).

Further, the surface of the curable resin layer (Z2) of the resin film forming sheet (II) is a surface to which the object to be processed is attached. The curable resin layer (Z2) is a curable resin layer, and a cured resin film can be formed by performing a curing treatment. The curing treatment may be performed in parallel with the predetermined processing, or may be performed after the predetermined processing is performed.

Then, the adhesive laminate of the present invention is subjected to heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles, whereby the adhesive sheet (I) and the base material of the resin film forming sheet (II) ( It can be separated at the interface P with Y2). In the following description, the heat treatment is also referred to as "separation heat treatment".
Therefore, using the adhesive laminate of the present invention, the object to be processed is fixed to the support, the object to be processed is subjected to a predetermined process, and then separated at the interface P by the heat treatment. It is possible to obtain a processed object with a resin film in which a resin film forming sheet (II) is laminated on the object.
Here, the object to be processed with a resin film may be an object to be processed with a cured resin film formed by curing the curable resin layer (Z2), and the curable resin layer (Z2) is uncured. It may be a processing object with a curable resin film.
In the following description, the "resin film" is a "curable resin film" formed by curing the curable resin layer (Z2) and a "curable resin film" in which the curable resin layer (Z2) is uncured. Both of "resin film" are shown.

1 to 3 are schematic cross-sectional views showing the configurations of the adhesive laminates of the first aspect, the second aspect, and the third aspect of the present invention, respectively. Hereinafter, the configuration of the adhesive laminate according to one aspect of the present invention will be described with reference to FIGS. 1 to 3 as appropriate.

<Adhesive laminate of the first aspect>
Examples of the adhesive laminate of the first aspect of the present invention include the adhesive laminates 1a and 1b shown in FIGS. 1A and 1B.
The adhesive laminates 1a and 1b are a resin film forming sheet having a base material (Y1) and a pressure-sensitive adhesive layer (X1) and a base material (Y2) and a curable resin layer (Z2). (II) is provided, and the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.

In the adhesive laminate of the present invention, any layer of the adhesive sheet (I) is a layer containing thermal expansion particles so that it can be separated at the interface P by heat treatment for separation.
In the adhesive laminate of the present invention, the heat-expandable particles expand by the heat treatment for separation, and the surface of the layer containing the heat-expandable particles becomes uneven. As a result, the contact area between the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) is reduced.
As a result, the object to be processed is attached on the surface of the curable resin layer (Z2) of the resin film forming sheet (II), and after performing the predetermined processing, the adhesive sheet (I) and the resin film forming sheet ( By separating the II) at the interface P with the base material (Y2), the object to be processed attached to the resin film forming sheet (II) can be obtained.

Therefore, in the adhesive laminate of the present invention, the object to be processed can be fixed to the support via the adhesive laminate to perform a predetermined process, and the process is performed after the predetermined process is performed. The object can be easily separated from the support at the interface P with a slight force. After separating from the support, a processed object with a resin film forming sheet can be obtained.
Therefore, the use of the adhesive laminate of the present invention has the following advantages, for example.
-In the next process, it is not necessary to attach the resin film forming sheet to the processed object after separation.
-Even when the object to be processed is thinned and fragile, the resin film forming sheet is attached to the object to be processed, so that support performance is given and the handleability such as transportation to the next process is good. Can be done.

In the first aspect of the present invention, the base material (Y1) has a heat-expandable base material layer (Y1-1) containing heat-expandable particles like the adhesive laminates 1a and 1b shown in FIG. Is preferable.
The base material (Y1) has a single-layer structure having only the heat-expandable base material layer (Y1-1) containing the heat-expandable particles, like the adhesive laminate 1a shown in FIG. 1 (a). You may.
Further, the base material (Y1) includes a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2) as shown in the adhesive laminate 1b shown in FIG. 1 (b). It may have a multi-layer structure having and.

In the adhesive laminate 1a shown in FIG. 1A, the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation, and the heat-expandable particles are expanded. The surface of the base material (Y1) on the resin film forming sheet (II) side is uneven, and the contact area between the base material (Y1) and the base material (Y2) of the resin film forming sheet (II) is reduced. ..
On the other hand, since the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate 1a is attached to the support, it is difficult for irregularities to be formed on the surface of the base material (Y1) on the pressure-sensitive adhesive layer (X1) side. As a result, unevenness can be efficiently formed on the surface of the base material (Y1) in contact with the resin film forming sheet (II).
As a result, the adhesive laminate 1a is easily put together at the interface P between the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) with a slight force. Can be separated into.
By forming the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate 1a from a pressure-sensitive adhesive composition that has a high adhesive force to the support, it can be more easily separated at the interface P. It is also possible to design.

Further, in the adhesive laminate 1b shown in FIG. 1B, the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation. However, the surface of the base material (Y1) on the resin film forming sheet (II) side is uneven, and the contact area between the base material (Y1) and the base material (Y2) of the resin film forming sheet (II) becomes large. Decrease.
On the other hand, since the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion due to heat treatment, the surface of the base material (Y1) on the pressure-sensitive adhesive layer (X1) side. It is difficult for unevenness to be formed on the surface. As a result, unevenness can be efficiently formed on the surface of the base material (Y1) on the resin film forming sheet (II) side.
As a result, the adhesive laminate 1b is easily put together at the interface P between the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) with a slight force. Can be separated into.

From the above viewpoint, in the first aspect of the present invention, as in the adhesive laminate 1b shown in FIG. (B), the base material (Y1) has a heat-expandable base material layer (Y1-1) on one surface side. It is preferable that the non-thermally expandable base material layer (Y1-2) is provided on the other surface side.

Further, in the first aspect of the present invention, from the viewpoint of forming an adhesive laminate that can be easily separated collectively at the interface P with a smaller force, the adhesive laminates 1a and 1b have an adhesive sheet (I). It is preferable that the heat-expandable base material layer (Y1-1) of the base material (Y1) and the base material (Y2) of the resin film forming sheet (II) are directly laminated.

<Adhesive laminate of the second aspect>
Examples of the adhesive laminate of the second aspect of the present invention include the adhesive laminates 1c and 1d shown in FIGS. 2 (a) and 2 (b).
The adhesive laminates 1c and 1d shown in FIG. 2 have a structure in which the adhesive sheet (I) has a base material (Y1) sandwiched between the first adhesive layer (X11) and the second adhesive layer (X12). However, it has a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
In the adhesive laminates 1c and 1d, the surface of the second adhesive layer (X12) is the surface to be attached to the support.

In the second aspect of the present invention, the base material (Y1) has a heat-expandable base material layer (Y1-1) containing heat-expandable particles, as in the adhesive laminates 1c and 1d shown in FIG. Is preferable.
The base material (Y1) has a single-layer structure having only a heat-expandable base material layer (Y1-1) containing heat-expandable particles, as in the adhesive laminate 1c shown in FIG. 2 (a). You may. Further, the base material (Y1) includes a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2) as shown in the adhesive laminate 1d shown in FIG. 2 (b). It may have a multi-layer structure having and.
Further, when the base material (Y1) has a multi-layer structure including a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2), the heat-expandable base material layer It is preferable that (Y1-1) is arranged on the resin film forming sheet (II) side, and the non-thermally expandable base material layer (Y1-2) is arranged on the second pressure-sensitive adhesive layer (X12) side.

In the adhesive laminate 1c shown in FIG. 2A, the heat-expandable particles in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation, and the first 1 The surface of the base material (Y1) on the pressure-sensitive adhesive layer (X11) side has irregularities. Then, the first pressure-sensitive adhesive layer (X11) is also pushed up by the unevenness generated on the surface of the base material (Y1), and the surface of the first pressure-sensitive adhesive layer (X11) on the resin film forming sheet (II) side also has unevenness. It is formed. As a result, the contact area between the first pressure-sensitive adhesive layer (X11) and the base material (Y2) of the resin film-forming sheet (II) is reduced.
On the other hand, since the second adhesive layer (X12) of the adhesive laminate 1c is attached to the support, the surface of the base material (Y1) on the second adhesive layer (X12) side has irregularities. Hard to form. Therefore, unevenness is efficiently formed on the surface of the base material (Y1) on the first adhesive layer (X11) side, and unevenness is likely to be formed on the surface of the first adhesive layer (X11).
As a result, the adhesive laminate 1c is lumped together with a slight force at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II). It can be easily separated.
By forming the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive laminate 1c from a pressure-sensitive adhesive composition that has a high adhesive force to the support, it can be more easily separated at the interface P. It is also possible to design.

Further, in the adhesive laminate 1d shown in FIG. 2B, the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation. However, the surface of the base material (Y1) on the first pressure-sensitive adhesive layer (X11) side is uneven. Then, the first pressure-sensitive adhesive layer (X11) is also pushed up by the unevenness generated on the surface of the base material (Y1), and the surface of the first pressure-sensitive adhesive layer (X11) on the resin film forming sheet (II) side also has unevenness. It is formed. As a result, the contact area between the first pressure-sensitive adhesive layer (X11) and the base material (Y2) of the resin film-forming sheet (II) is reduced.
On the other hand, since the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion due to heat treatment, the base material (Y1) is on the second pressure-sensitive adhesive layer (X12) side. It is difficult for irregularities to be formed on the surface of the surface. As a result, unevenness can be efficiently formed on the surface of the base material (Y1) on the first pressure-sensitive adhesive layer (X11) side.
As a result, the adhesive laminate 1d is easily formed at the interface P between the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) at once with a slight force. Can be separated into.

Here, also in the second aspect of the present invention, from the viewpoint of forming an adhesive laminate that can be easily separated at the interface P with a smaller force, the adhesive laminates 1c and 1d are the adhesive sheets (I). The heat-expandable base material layer (Y1-1) of the base material (Y1) and the first pressure-sensitive adhesive layer (X11) are preferably laminated directly. In this case, it is more preferable that the first pressure-sensitive adhesive layer (X11) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.

<Adhesive laminate of the third aspect>
The adhesive laminates 1a and 1b of the first aspect of the present invention and the adhesive laminates 1c and 1d of the second aspect of the present invention are all thermally expanded as one of the layers constituting the base material (Y1). It contains a layer containing sex particles.
On the other hand, as the adhesive laminate of the third aspect of the present invention, a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles is provided on the surface of the base material (Y1) of the pressure-sensitive adhesive sheet (I) on the interface P side. , A non-thermally expandable pressure-sensitive adhesive layer may be provided on the other surface of the base material (Y1).
In such an embodiment, for example, as in the adhesive laminate 2 shown in FIG. 3, the adhesive sheet (I) is made of a base material (X12) by a first adhesive layer (X11) and a second adhesive layer (X12). The first pressure-sensitive adhesive layer (X11) has a structure in which Y1) is sandwiched, the first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles, and the second pressure-sensitive adhesive layer (X12) is non-heat-expandable. Examples of the pressure-sensitive adhesive layer include those having a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
In the above configuration such as the adhesive laminate 2, the surface of the second adhesive layer (X12) is a surface to be attached to the support.
Further, in the above configuration such as the adhesive laminate 2, the base material (Y1) is preferably a non-thermally expandable base material.

In the adhesive laminate 2 shown in FIG. 3, the surface of the heat-expandable adhesive layer, which is the first adhesive layer (X11), is uneven due to the heat treatment for separation, and the adhesive layer 2 and the first adhesive layer (X11) The contact area of the resin film forming sheet (II) with the base material (Y2) is reduced.
On the other hand, the surface of the first pressure-sensitive adhesive layer (X11) on the base material (Y1) side is less likely to have irregularities because the base material (Y1), which is a non-thermally expandable base material, is laminated. Therefore, unevenness is efficiently formed on the surface of the first pressure-sensitive adhesive layer (X11) on the resin film-forming sheet (II) side.
As a result, the adhesive laminate 2 is integrated with a slight force at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II). It can be easily separated.

<Structure of adhesive laminate with release material>
In the adhesive laminate of one aspect of the present invention, the adhesive layer (X1) to which the support is attached and the surface of the curable resin layer (Z2) to which the object to be processed are attached are further peeled off. It may be a structure in which materials are laminated.
For example, in the adhesive laminates 1a and 1b shown in FIGS. 1A and 1B, the adhesive surfaces of one of the adhesive layer (X1) and the curable resin layer (Z2) are peeled off on both sides. A roll-shaped structure may be obtained in which the release material is laminated. The adhesive laminates 1c and 1d shown in FIGS. 2 (a) and 2 (b) and the adhesive laminate 2 shown in FIG. 3 may also be wound in a roll shape in the same manner.

[Various physical characteristics of adhesive laminate]
The adhesive laminate according to one aspect of the present invention is a base material of the adhesive sheet (I) and the resin film forming sheet (II) by heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles. At the interface P with (Y2), it can be easily separated at once with a small force.
Here, in the adhesive laminate of one aspect of the present invention, the peeling force (F ₁ ) at the time of separation at the interface P by heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles is , Usually 0 to 2000 mN / 25 mm, preferably 0 to 1000 mN / 25 mm, more preferably 0 to 150 mN / 25 mm, still more preferably 0 to 100 mN / 25 mm, still more preferably 0 to 50 mN / 25 mm.
When the peeling force (F ₁ ) is 0 mN / 25 mm, even if the peeling force is measured by the method described in the examples, the peeling force may be too small to be measured.

Further, from the viewpoint of sufficiently fixing the object to be processed before the heat treatment so as not to adversely affect the processing work, the base material (Y2) of the adhesive sheet (I) and the resin film forming sheet (II). It is preferable that the interlayer adhesion with the above is high.
From the above viewpoint, in the adhesive laminate of one aspect of the present invention, the peeling force (F ₀ ) at the time of separation at the interface P before the heat treatment is preferably 100 mN / 25 mm or more, more preferably 130 mN. / 25 mm or more, more preferably 160 mN / 25 mm or more, and preferably 50,000 mN / 25 mm or less.

In the adhesive laminate of one aspect of the present invention, the peeling force (F ₀ ) is larger than the peeling force (F ₁ ). Specifically, the ratio [(F ₁ ) / (F ₀ )] of the peeling force (F ₁ ) to the peeling force (F ₀ ) is preferably _{0 to} 0.9, more preferably 0 to 0.8. , More preferably 0 to 0.5, and even more preferably 0 to 0.2.

The temperature condition for measuring the peeling force (F ₁ ) may be a temperature equal to or higher than the expansion start temperature (t) and the temperature at which the thermally expandable particles expand.
The temperature condition for measuring the peeling force (F ₀ ) may be less than the expansion start temperature (t), but is basically room temperature (23 ° C.).
However, more specific measurement conditions and measurement methods for the peeling force (F ₁ ) and the peeling force (F ₀ ) are based on the methods described in the examples.

In the adhesive laminate according to one aspect of the present invention, the pressure-sensitive adhesive layer (X1) (first pressure-sensitive adhesive layer (X11) and second pressure-sensitive adhesive layer (X12)) of the pressure-sensitive adhesive sheet (I) at room temperature (23 ° C.). ) 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, still more preferably 0. It is .5-4.0 N / 25 mm.
When the pressure-sensitive adhesive sheet (I) has a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), the adhesive strengths of the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are different, respectively. The above range is preferable, but from the viewpoint of improving the adhesiveness with the support and making it easier to separate all at once at the interface P, the second pressure-sensitive adhesive layer (X12) to be attached to the support It is more preferable that the adhesive strength is higher than the adhesive strength of the first pressure-sensitive adhesive layer (X11).

Further, in the adhesive laminate of one aspect of the present invention, from the viewpoint of improving the adhesion to the object to be processed to be attached, the surface of the curable resin layer (Z2) of the resin film forming sheet (II). However, it is preferable that it has adhesiveness.
Specifically, the adhesive strength of the curable resin layer (Z2) of the resin film forming sheet (II) at room temperature (23 ° C.) is preferably 0.01 to 5 N / 25 mm, more preferably 0. It is 05 to 4N / 25mm, more preferably 0.1 to 3N / 25mm.

In the present specification, the adhesive strength of the pressure-sensitive adhesive layer (X1) (first pressure-sensitive adhesive layer (X11) and second pressure-sensitive adhesive layer (X12)) and the curable resin layer (Z2) are described in Examples. Means the value measured by the described method.

The base material (Y1) contained in the adhesive sheet (I) and the base material (Y2) contained in the resin film forming sheet (II) are non-adhesive base materials.
In the present invention, whether or not the substrate is a non-adhesive substrate is determined if the probe tack value measured in accordance with JIS Z0237: 1991 with respect to the surface of the substrate of interest is less than 50 mN / 5 mmφ. The base material is judged to be a "non-adhesive base material".
The probe tack values on the surfaces of the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) and the base material (Y2) contained in the resin film forming sheet (II) used in one aspect of the present invention are usually 50 mN / It is less than 5 mmφ, but preferably less than 30 mN / 5 mmφ, more preferably less than 10 mN / 5 mmφ, and even more preferably less than 5 mN / 5 mmφ.
In addition, in this specification, the specific measurement method of the probe tack value on the surface of a heat-expandable base material is by the method described in Example.

Hereinafter, each layer constituting the adhesive laminate of the present invention will be described.

[Structure of adhesive sheet (I)]
The pressure-sensitive adhesive sheet (I) contained in the adhesive laminate of the present invention has a base material (Y1) and a pressure-sensitive adhesive layer (X1), and is subjected to a heat treatment for separation to form a base material (II) for forming a resin film. A heat-expandable pressure-sensitive adhesive sheet containing heat-expandable particles in any of the layers so that it can be separated at the interface with Y2).
In one aspect of the present invention, the thermal expansion start temperature (t) of the thermally expandable particles is preferably 60 to 270 ° C.

As the pressure-sensitive adhesive sheet (I) used in one aspect of the present invention, the following aspects are preferable.
The pressure-sensitive adhesive sheet (I) of the first aspect: The pressure-sensitive adhesive sheet (I) having a heat-expandable base material layer (Y1-1) containing heat-expandable particles as the base material (Y1).
-Adhesive sheet (I) of the second aspect: On both sides of the base material (Y1), a first pressure-sensitive adhesive layer (X11) which is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles and a non-heat-expandable adhesive An adhesive sheet (I) having a second adhesive layer (X12) which is an agent layer.
-Adhesive sheet (I) in which the base material (Y1) is a non-thermally expandable base material.
Hereinafter, the pressure-sensitive adhesive sheets (I) of the first aspect and the second aspect used in one aspect of the present invention will be described.

<Adhesive sheet (I) of the first aspect>
As the pressure-sensitive adhesive sheet (I) of the first aspect, as shown in FIGS. 1 and 2, the base material (Y1) has a heat-expandable base material layer (Y1-1) containing heat-expandable particles. Be done.

In the pressure-sensitive adhesive sheet (I) of the first aspect, the viewpoint that the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) can be easily separated together with a slight force at the interface P. Therefore, the pressure-sensitive adhesive layer (X1) is preferably a non-thermally expandable pressure-sensitive adhesive layer.
Specifically, in the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminates 1a and 1b shown in FIG. 1, the pressure-sensitive adhesive layer (X1) is preferably a non-thermally expandable pressure-sensitive adhesive layer. Further, in the adhesive sheet (I) of the adhesive laminates 1c and 1d shown in FIG. 2, both the first adhesive layer (X11) and the second adhesive layer (X12) are non-thermally expandable adhesive. It is preferably an agent layer.

The thickness of the base material (Y1) before the heat treatment for separation of the pressure-sensitive adhesive sheet (I) of the first aspect is preferably 10 to 1000 μm, more preferably 20 to 700 μm, still more preferably 25 to 500 μm, still more preferably. It is 30 to 300 μm.

The thickness of the pressure-sensitive adhesive layer (X1) before the heat treatment for separation of the pressure-sensitive adhesive sheet (I) of the first aspect is preferably 1 to 60 μm, more preferably 2 to 50 μm, still more preferably 3 to 40 μm, still more preferably. Is 5 to 30 μm.

In the present specification, for example, as shown in FIG. 2, when the adhesive sheet (I) has a plurality of adhesive layers, the above-mentioned "thickness of the adhesive layer (X1)" is the respective adhesive. It means the thickness of the agent layer (in FIG. 2, the thickness of each of the pressure-sensitive adhesive layers (X11) and (X12)).
Further, in the present specification, the thickness of each layer constituting the adhesive laminate means a value measured by the method described in Examples.

In the pressure-sensitive adhesive sheet (I) of the first aspect, the thickness ratio of the heat-expandable base material layer (Y1-1) and the pressure-sensitive adhesive layer (X1) before the heat treatment for separation [(Y1-1) / (X1). )] Is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, still more preferably 30 or less.
When the thickness ratio is 1000 or less, the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) can be easily separated at the interface P with a slight force by heat treatment. It can be a possible adhesive laminate.
The thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and even more preferably 5.0 or more.

Further, in the pressure-sensitive adhesive sheet (I) of the first aspect, the base material (Y1) is composed of only the heat-expandable base material layer (Y1-1) as shown in FIG. 1 (a). Also, as shown in FIG. 1 (b), the resin film forming sheet (II) side has a heat-expandable base material layer (Y1-1), and the pressure-sensitive adhesive layer (X1) side has a non-thermally expandable material layer. It may have a base material layer (Y1-2).

In the pressure-sensitive adhesive sheet (I) of the first aspect, the thickness ratio of the heat-expandable base material layer (Y1-1) and the non-heat-expandable base material layer (Y1-2) before the heat treatment for separation [(Y1). -1) / (Y1-2)] is preferably 0.02 to 200, more preferably 0.03 to 150, and even more preferably 0.05 to 100.

<Adhesive sheet (I) of the second aspect>
As the pressure-sensitive adhesive sheet (I) of the second aspect, as shown in FIG. 3, a first pressure-sensitive adhesive layer which is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles on both side surfaces of the base material (Y1), respectively. (X11) and those having a second pressure-sensitive adhesive layer (X12) which is a non-thermally expandable pressure-sensitive adhesive layer can be mentioned.
In the pressure-sensitive adhesive sheet (I) of the second aspect, the first pressure-sensitive adhesive layer (X11), which is a heat-expandable pressure-sensitive adhesive layer, and the base material (Y2) of the resin film-forming sheet (II) are in direct contact with each other. ..
In the pressure-sensitive adhesive sheet (I) of the second aspect, the base material (Y1) is preferably a non-thermally expandable base material layer.

In the pressure-sensitive adhesive sheet (I) of the second aspect, the first pressure-sensitive adhesive layer (X11) which is a heat-expandable pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer which is a non-heat-expandable pressure-sensitive adhesive layer before the heat treatment for separation. The thickness ratio [(X11) / (X12)] to (X12) is preferably 0.1 to 80, more preferably 0.3 to 50, and even more preferably 0.5 to 15.

Further, in the pressure-sensitive adhesive sheet (I) of the second aspect, the thickness ratio of the first pressure-sensitive adhesive layer (X11), which is the heat-expandable pressure-sensitive adhesive layer, and the base material (Y1) before the heat treatment for separation [( X11) / (Y1)] is preferably 0.05 to 20, more preferably 0.1 to 10, and even more preferably 0.2 to 3.

Hereinafter, the heat-expandable particles contained in any of the layers constituting the pressure-sensitive adhesive sheet (I) will be described, and then the heat-expandable base material layer (Y1-1) constituting the base material (Y1) and non-thermally expandable particles will be described. The sex substrate layer (Y1-2) and the pressure-sensitive adhesive layer (X1) will be described in detail.

<Thermal expandable particles>
The thermally expandable particles used in the present invention may be particles that expand by heating, but are preferably particles whose expansion start temperature (t) is adjusted to 60 to 270 ° C. The expansion start temperature (t) is appropriately selected depending on the use of the adhesive laminate.
In addition, in this specification, the expansion start temperature (t) of a heat-expandable particle means a value measured based on the following method.

(Measurement method of expansion start temperature (t) of thermally expandable particles)
To an aluminum cup with a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, 0.5 mg of the heat-expandable particles to be measured were added, and an aluminum lid (diameter 5.6 mm, thickness 0. Prepare a sample on which 1 mm) is placed.
Using a dynamic viscoelasticity measuring device, the height of the sample is measured with a force of 0.01 N applied by a pressurizer from the upper part of the aluminum lid to the sample. And. With a force of 0.01 N applied by the pressurizer, it is heated from 20 ° C. to 300 ° C. at a heating rate of 10 ° C./min, the amount of displacement of the pressurizer in the vertical direction is measured, and displacement in the positive direction is started. Let the temperature be the expansion start temperature (t).

The heat-expandable particles are microencapsulated foaming agents composed of an outer shell made of a thermoplastic resin and an contained component contained in the outer shell and vaporized when heated to a predetermined temperature. It is preferable to have.
Examples of the thermoplastic resin constituting the outer shell of the microencapsulating foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone and the like.

Examples of the contained components contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptan, isooctane, isononan, isodecane, cyclopropane, cyclobutane, and cyclopentane. , Cyclohexane, cycloheptan, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, isotoridecan, 4-methyldodecane, isotetradecane, isopentadecane, iso Hexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecan, isonanodecane, 2,6,10,14-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 heat-expandable particles can be adjusted by appropriately selecting the type of the inclusion component.

The average particle size of the heat-expandable particles used in one embodiment of the present invention before expansion at 23 ° C. is preferably 3 to 100 μm, more preferably 4 to 70 μm, still more preferably 6 to 60 μm, still more preferably 10 to 10. It is 50 μm.
The average particle size of the heat-expandable particles before expansion is the volume median particle size (D ₅₀ ), and is a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name “Mastersizer 3000”). In the particle distribution of the heat-expandable particles before expansion, the cumulative volume frequency calculated from the smaller particle size of the heat-expandable particles before expansion means the particle size corresponding to 50%.

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

The maximum volume expansion rate when the thermally expandable particles used in one embodiment of the present invention are 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 further. It is preferably 2.5 to 60 times, and even more preferably 3 to 40 times.

<Thermal expansion base layer (Y1-1)>
In the adhesive laminate of one aspect of the present invention, when the base material (Y1) of the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) containing heat-expandable particles, a heat-expandable group. The material layer (Y1-1) preferably satisfies the following requirement (1).
- Requirement (1): in the expansion starting temperature of the thermally expandable particles (t), thermally expandable base layer storage modulus (Y1-1) E '(t) is at 1.0 × ¹⁰ 7 Pa or less is there.
In the present specification, the storage elastic modulus E'of the heat-expandable base material layer (Y1-1) at a predetermined temperature means a value measured by the method described in Examples.

The above requirement (1) can be said to be an index showing the rigidity of the heat-expandable base material layer (Y1-1) immediately before the heat-expandable particles expand.
Before the expansion of the thermally expandable particles, the storage elastic modulus E'of the thermally expandable base material layer (Y1-1) decreases as the temperature rises. However, before and after reaching the expansion start temperature (t) of the thermally expandable particles, the thermally expandable particles start to expand, so that the storage elastic modulus E'of the thermally expandable base material layer (Y1-1) decreases. It is suppressed.
On the other hand, in order to enable easy separation at the interface P between the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) with a slight force, the expansion start temperature (t) or higher It is necessary to easily form irregularities on the surface of the pressure-sensitive adhesive sheet (I) on the side where the base material (Y2) is laminated by heating to the temperature of.
That is, in the heat-expandable base material layer (Y1-1) that satisfies the above requirement (1), the heat-expandable particles expand at the expansion start temperature (t) and become sufficiently large, and the resin film forming sheet (II) Concavities and convexities are likely to be formed on the surface of the pressure-sensitive adhesive sheet (I) on the side where the base material (Y2) is laminated.
As a result, it can be an adhesive laminate that can be easily separated with a slight force at the interface P between the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II).

From the above viewpoint, the storage elastic modulus E'(t) specified in the requirement (1) of the thermally expandable base material layer (Y1-1) used in the present invention is preferably 9.0 × 10 ⁶ Pa or less, more preferably. Is 8.0 × 10 ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.
Further, the flow of the expanded thermally expandable particles is suppressed, and the shape of the unevenness formed on the surface of the adhesive sheet (I) on the side where the resin film forming sheet (II) is laminated with the base material (Y2) is maintained. From the viewpoint of improving the properties and making it easier to separate at the interface P with a slight force, the storage elastic modulus E'(t) specified in the requirement (1) of the heat-expandable substrate layer (Y1-1) is It is preferably 1.0 × 10 ³ Pa or more, more preferably 1.0 × 10 ⁴ Pa or more, and further preferably 1.0 × 10 ⁵ Pa or more.

From the viewpoint of forming the heat-expandable base material layer (Y1-1) satisfying the above requirement (1), the content of the heat-expandable particles in the heat-expandable base material layer (Y1-1) is the heat-expandable base material. With respect to the total mass (100% by mass) of the layer (Y1-1), preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, still more preferably 15 to It is 25% by mass.

From the viewpoint of improving the interlayer adhesion between the heat-expandable base layer (Y1-1) and other layers to be laminated, the surface of the heat-expandable base layer (Y1-1) is subjected to an oxidation method. Surface treatment by an unevenness method or the like, 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), hot air treatment, ozone, and ultraviolet irradiation treatment, and examples of the unevenness method include sandblasting method and solvent treatment method. And so on.

The heat-expandable base material layer (Y1-1) is preferably formed from the resin composition (y) containing the resin and the heat-expandable particles.
The resin composition (y) may contain an additive for a base material, if necessary, as long as the effects of the present invention are not impaired.
Examples of the base material additive include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
These base material additives may be used alone or in combination of two or more.
When these base material additives are contained, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the resin. It is 10 parts by mass.

The heat-expandable particles contained in the resin composition (y), which is a material for forming the heat-expandable base material layer (Y1-1), are as described above.
The content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 with respect to the total amount (100% by mass) of the active ingredient of the resin composition (y). It is ~ 30% by mass, more preferably 15 to 25% by mass.

The resin contained in the resin composition (y) which is the material for forming the heat-expandable base material layer (Y1-1) may be a non-adhesive resin or an adhesive resin.
That is, even if the resin contained in the resin composition (y) is an adhesive resin, the adhesive resin is used in the process of forming the heat-expandable base material layer (Y1-1) from the resin composition (y). It is sufficient that the resin obtained by polymerizing with the polymerizable compound becomes a non-adhesive resin, and the heat-expandable base material layer (Y1-1) containing the resin becomes non-adhesive.

The mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 10 to 1,000,000, more preferably 10 to 700,000, and even more preferably 10 to 500,000.
When the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer can be used. It may be.

The content of the resin is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, based on the total amount (100% by mass) of the active ingredient of the resin composition (y). %, More preferably 70 to 85% by mass.

From the viewpoint of forming the heat-expandable base material layer (Y1-1) satisfying the above requirement (1), the resin contained in the resin composition (y) is selected from acrylic urethane-based resin and olefin-based resin. It is preferable to include one or more kinds of
Further, as the acrylic urethane resin, the following resin (U1) is preferable.
An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester.

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

Examples of the polyol which is 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.
As the polyol used in one embodiment of the present invention, a diol is preferable, an ester type diol, an alkylene type diol and a carbonate type diol are more preferable, and an ester type diol and a carbonate type diol are further preferable.

Examples of the ester-type diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, and the like. One or more selected from diols such as diethylene glycol, alkylene glycol such as dipropylene glycol; and phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hetic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexa Examples thereof include dicarboxylic acids such as hydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid and methylhexahydrophthalic acid, and one or more selected from these anhydrides.
Specifically, polyethylene adipatediol, polybutylene adipatediol, polyhexamethylene adipatediol, polyhexamethyleneisophthalatediol, polyneopentyl adipatediol, polyethylenepropylene adipatediol, polyethylenebutylene adipatediol, polybutylenehexamethylene adipatediol, 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 Examples thereof include pentyl terephthalate diol.

Examples of the alkylene-type diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, and the like. Examples thereof include alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; and 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 polyisocyanate used as a raw material for the urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
These multivalent isocyanates may be used alone or in combination of two or more.
Further, these polyvalent isocyanates may be a trimethylolpropan adduct-type modified product, a Biuret-type modified product reacted with water, or an isocyanurate-type modified product containing an isocyanurate ring.

Among these, as the polyvalent isocyanate used in one aspect of the present invention, diisocyanate is preferable, 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-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexane. Examples thereof include diisocyanate, methyl-2,4-cyclohexanediisocyanate and methyl-2,6-cyclohexanediisocyanate, but isophorone diisocyanate (IPDI) is preferable.

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

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. Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

The vinyl compound that becomes the side chain of the acrylic urethane resin (U1) contains at least (meth) acrylic acid ester.
As the (meth) acrylic acid ester, one or more selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is preferable, and alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are more preferably used in combination.

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

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

Examples of the hydroxyalkyl (meth) acrylate include the same hydroxyalkyl (meth) acrylate used for introducing ethylenically unsaturated groups into both ends of the above-mentioned linear urethane prepolymer.

Examples of vinyl compounds other than (meth) acrylic acid ester include 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. , (Meta) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, polar group-containing monomers such as meta (acrylamide); and the like.
These may be used alone or in combination of two or more.

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

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

The acrylic urethane resin (U1) used in one embodiment of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester and polymerizing both.
The polymerization is preferably carried out by further adding a radical initiator.

In the acrylic urethane resin (U1) used in one aspect 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 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and even more preferably 35 in terms of mass ratio. / 65-55 / 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 thereof include ethylene, propylene, butylene, isobutylene, and 1-hexene.
Among these, ethylene and propylene are preferable.

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 and less than 942 kg / m ³ ), high density polyethylene (HDPE, density: 942 kg / m ³ or more), linear low density polyethylene and other polyethylene resins; polypropylene resin (PP); Polybutene resin (PB); Ethylene-propylene copolymer; Olefin-based elastomer (TPO); Poly (4-methyl-1-pentene) (PMP); Ethylene-vinyl acetate copolymer (EVA); Ethylene -Vinyl alcohol copolymer (EVOH); olefin-based ternary copolymer such as ethylene-propylene- (5-ethylidene-2-norbornene); and the like.

In one aspect of the present invention, the olefin-based resin may be a modified olefin-based resin further subjected to one or more modifications selected from acid modification, hydroxyl group modification, and acrylic modification.

For example, the acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin is a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof with the above-mentioned non-modified olefin-based resin. Can be mentioned.
Examples of the unsaturated carboxylic acid or its anhydride 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, norbornendicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like.
The unsaturated carboxylic acid or its anhydride 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 acrylic modification is a modification obtained by graft-polymerizing an alkyl (meth) acrylate as a side chain to the above-mentioned non-modified olefin-based resin which is the main chain. Polymers can be mentioned.
The alkyl group of the above alkyl (meth) acrylate has preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and further preferably 1 to 12 carbon atoms.
Examples of the above-mentioned alkyl (meth) acrylate include the same compounds as those that can be selected as the monomer (a1') described later.

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 on the above-mentioned non-modified olefin resin which is the main chain.
Examples of the above-mentioned hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. Hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol can be mentioned.

(Resin other than acrylic urethane resin and olefin resin)
In one aspect 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; acrylonitrile-butadiene-styrene co-weight. Combined; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resin; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; Fluorine-based resin and the like can be mentioned.

However, from the viewpoint of forming the thermally expandable base material layer (Y1-1) satisfying the above requirement (1), the content ratio of the acrylic urethane resin and the resin other than the olefin resin in the resin composition (y) is determined. Less is 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 with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, still more preferably less than 1 part by mass.

(Solvent-free resin composition (y1))
As one aspect of the resin composition (y) used in one aspect 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-mentioned thermal expansion property Examples thereof include a solvent-free resin composition (y1) in which particles are blended and no solvent is blended.
In the solvent-free 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 energy rays, it is easy to form a heat-expandable base material layer (Y1-1) satisfying the above requirement (1).

The types, shapes, and blending amounts (contents) of the heat-expandable particles blended in the solvent-free resin composition (y1) are as described above.

The mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1000 to 50,000, more preferably 2000 to 40,000, still more preferably 3000 to 35,000, and more. More preferably, it is 4000 to 30000.

The oligomer may be any resin contained in the above-mentioned resin composition (y) having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less, and the above-mentioned urethane prepolymer (UP). ) Is preferable.
As the oligomer, a modified olefin resin having an ethylenically unsaturated group can also be used.

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

Examples of the energy ray-polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, and adamantan (). Alicyclic polymerizable compounds such as meta) acrylates and tricyclodecane acrylates; aromatic polymerizable compounds such as phenylhydroxypropyl acrylates, benzyl acrylates and phenolethylene oxide modified acrylates; tetrahydrofurfuryl (meth) acrylates, morpholine acrylates, N- Examples thereof include 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 content ratio [oligomer / energy ray-polymerizable monomer] of the oligomer to the energy ray-polymerizable monomer in the solvent-free resin composition (y1) is a mass ratio, preferably 20/80 to 90 /. 10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.

In one aspect of the present invention, the solvent-free resin composition (y1) is preferably further blended with 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 sulfate, tetramethylthium monosulfide, and azobisisobutyrol. Examples thereof include nitrile, dibenzyl, diacetyl, 8-chloranthraquinone and the like.
These photopolymerization initiators may be used alone or in combination of two or more.

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

<Non-thermally expandable base material layer (Y1-2)>
Examples of the material for forming the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) include paper materials, resins, metals, etc., and the adhesive laminate according to one aspect of the present invention. It can be appropriately selected according to the application.

Examples of the paper material include thin leaf paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, parchment paper, and glassin paper.
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 and poly. 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 ether ketone; Polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; fluorine resin and the like can be mentioned.
Examples of the metal include aluminum, tin, chromium, titanium and the like.

These forming materials may be composed of one kind, or two or more kinds may be used in combination.
As the non-thermally expandable base material layer (Y1-2) in which two or more kinds of forming materials are used in combination, a paper material laminated with a thermoplastic resin such as polyethylene, or a metal on the surface of a resin film or sheet containing the resin. Examples thereof include those having a film formed.
As a method for forming the metal layer, for example, a method of vapor-depositing the metal by a PVD method such as vacuum vapor deposition, sputtering, or ion plating, or a method of attaching a metal foil made of the metal by using a general adhesive. The method of doing this can be mentioned.

When the non-thermally expandable base material layer (Y1-2) contains a resin, it is not used from the viewpoint of improving the interlayer adhesion between the non-thermally expandable base material layer (Y1-2) and other layers to be laminated. Similar to the above-mentioned heat-expandable base material layer (Y1-1), the surface of the heat-expandable base material layer (Y1-2) is also subjected to surface treatment by an oxidation method, an unevenness method, etc. Alternatively, primer treatment may be performed.

When the non-thermally expandable base material layer (Y1-2) contains a resin, the above-mentioned base material additive that can be contained in the resin composition (y) may be contained together with the resin.

The non-thermally expandable base material layer (Y1-2) is a non-thermally expandable layer determined based on the above method.
Therefore, the volume change rate (%) of the non-thermally expandable base material layer (Y1-2) calculated from the above formula is less than 5%, but preferably less than 2%, more preferably less than 1%. , More preferably less than 0.1%, even more preferably less than 0.01%.

Further, the non-thermally expandable base material layer (Y1-2) 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-thermally expandable base material layer (Y1-2), it is possible to adjust the volume change rate within the above range even if the thermally expandable particles are contained. ..
However, the smaller the content of the thermally expandable particles in the non-thermally expandable base material layer (Y1-2), the more preferable.
The specific content of the heat-expandable particles is usually less than 3% by mass, preferably less than 1% by mass, based on the total mass (100% by mass) of the non-heat-expandable base material layer (Y1-2). It is more preferably less than 0.1% by mass, further preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.

<Adhesive layer (X1)>
The pressure-sensitive adhesive layer (X1) contained in the pressure-sensitive adhesive sheet (I) used in one aspect of the present invention can be formed from the pressure-sensitive adhesive composition (x1) containing a pressure-sensitive adhesive resin.
Further, the pressure-sensitive adhesive composition (x1) may contain an additive for a pressure-sensitive adhesive such as a cross-linking agent, a pressure-sensitive adhesive, a polymerizable compound, and a polymerization initiator, if necessary.
Hereinafter, each component contained in the pressure-sensitive adhesive composition (x1) will be described.
Even when the pressure-sensitive adhesive sheet (I) has a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are also present. , Can be formed from the pressure-sensitive adhesive composition (x1) containing each of the following components.

(Adhesive resin)
The adhesive resin used in one embodiment of the present invention may be a polymer having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
The mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and further preferably 30,000 from the viewpoint of improving the adhesive strength. ~ 1 million.

Specific examples of the adhesive resin include rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based 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 kinds of structural units, the form of the copolymer is not particularly limited, and block copolymers, random copolymers, and graft copolymers are used. It may be any of the polymers.

The adhesive resin used in one aspect of the present invention may be an energy ray-curable adhesive resin in which a polymerizable functional group is introduced into the side chain of the adhesive resin.
Examples of the polymerizable functional group include a (meth) acryloyl group and a vinyl group.
Further, examples of the energy ray include ultraviolet rays and electron beams, but ultraviolet rays are preferable.

In one aspect of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
When the pressure-sensitive adhesive sheet (I) having the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) is used, the first pressure-sensitive adhesive layer (X11) in contact with the resin film-forming sheet (II). ) Contains an acrylic resin, which makes it easier to form irregularities on the surface of the first pressure-sensitive adhesive layer.

The content ratio of the acrylic resin in the adhesive resin is preferably 30 to 100 with respect to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x1) or the adhesive layer (X1). It is by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass.

(Acrylic resin)
In one aspect of the present invention, the acrylic resin that can be used as the adhesive resin includes, for example, a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a cyclic structure. Examples thereof include polymers containing a structural unit derived from (meth) acrylate having.

The mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, and even more preferably 500,000 to 1,100,000. ..

The acrylic resin used in one embodiment of the present invention includes a structural unit (p1) derived from an alkyl (meth) acrylate (p1') (hereinafter, also referred to as "monomer (p1')") and a functional group-containing monomer (p2). An acrylic copolymer (P) having a structural unit (p2) derived from') (hereinafter, also referred to as "monomer (p2')") is more preferable.

The number of carbon atoms of the alkyl group contained in the monomer (p1') is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and even more preferably 4 to 8 from the viewpoint of improving adhesive properties. Is.
The alkyl group contained in the monomer (p1') may be a straight chain alkyl group or a branched chain alkyl group.

Examples of the monomer (p1') include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (). Examples thereof include meta) acrylate and stearyl (meth) acrylate.
These monomers (p1') may be used alone or in combination of two or more.
As the monomer (p1'), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.

The content of the structural unit (p1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (P). %, More preferably 70 to 97.0% by mass, even more preferably 80 to 95.0% by mass.

Examples of the functional group contained in the monomer (p2') include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
That is, examples of the monomer (p2') include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
These monomers (p2') may be used alone or in combination of two or more.
Among these, as the monomer (p2'), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.

Examples of the hydroxyl group-containing monomer include the same hydroxyl group-containing compounds as described above.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid, and their anhydrides. , 2- (Acryloyloxy) ethyl succinate, 2-carboxyethyl (meth) acrylate and the like.

The content of the structural unit (p2) is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, based on the total structural units (100% by mass) of the acrylic copolymer (P). %, More preferably 1.0 to 30% by mass, still more preferably 3.0 to 25% by mass.

The acrylic copolymer (P) may further have a structural unit (p3) derived from a monomer (p3') other than the monomer (p1') and (p2').
In the acrylic copolymer (P), the content of the structural units (p1) and (p2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (P). ~ 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.

Examples of the monomer (p3') include olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate. (Meta) Acrylate; Examples thereof include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholin, and N-vinylpyrrolidone.

Further, the acrylic copolymer (P) may be an energy ray-curable acrylic copolymer in which a polymerizable functional group is introduced into the side chain.
The polymerizable functional group and the energy ray are as described above.
The polymerizable functional group is a substituent capable of binding to an acrylic copolymer having the above-mentioned structural units (p1) and (p2) and a functional group having the structural unit (p2) of the acrylic copolymer. It can be introduced by reacting with a compound having a polymerizable functional group.
Examples of the compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.

(Crosslinking agent)
In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains a pressure-sensitive adhesive resin having a functional group like the above-mentioned acrylic copolymer (P), it may further contain a cross-linking agent. preferable.
The cross-linking agent reacts with a tacky resin having a functional group to crosslink the tacky resins with the functional group as a cross-linking starting point.

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

The content of the cross-linking agent is appropriately adjusted according to the number of functional groups of 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 functional groups. It is more preferably 0.03 to 7 parts by mass, and further preferably 0.05 to 5 parts by mass.

(Adhesive imparting agent)
In one aspect of the present invention, the pressure-sensitive adhesive composition (x1) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
In the present specification, the "tackiness-imparting agent" refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, which is a component that supplementarily improves the adhesive strength of the above-mentioned adhesive resin, and refers to the above-mentioned adhesion. It is distinguished from the sex resin.
The mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 500 to 8000, and even more preferably 800 to 5000.

As the tackifier, for example, it is obtained by copolymerizing a C5 distillate such as rosin resin, terpene resin, styrene resin, penten, isoprene, piperin, 1,3-pentadiene produced by thermal decomposition of petroleum naphtha. Examples thereof include C5-based petroleum resins, C9-based petroleum resins obtained by copolymerizing C9 distillates such as inden and vinyl toluene produced by thermal decomposition of petroleum naphtha, and hydrides obtained by hydrogenating these.

The softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and even more preferably 70 to 150 ° C.
In the present specification, the "softening point" of the tackifier means a value measured in accordance with JIS K 2531.
The tackifier may be used alone or in combination of two or more having different softening points and structures.
When two or more kinds of tackifiers are used, it is preferable that the weighted average of the softening points of the plurality of tackifiers belongs to the above range.

The content of the tackifier is preferably 0.01 to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x1) or the total mass (100% by mass) of the pressure-sensitive adhesive layer (X1). 65% by mass, more preferably 0.05 to 55% by mass, still more preferably 0.1 to 50% by mass, still more preferably 0.5 to 45% by mass, still more preferably 1.0 to 40% by mass. is there.

(Photopolymerization initiator)
In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains an energy ray-curable pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin, it is preferable to further contain 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 the same ones that are blended in the solvent-free resin composition (y1) described above.

The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and even more preferably 0, with respect to 100 parts by mass of the energy ray-curable adhesive resin. It is 05 to 2 parts by mass.

(Additives for adhesives)
In one aspect of the present invention, the pressure-sensitive adhesive composition (x1) contains an additive for a pressure-sensitive adhesive used in a general pressure-sensitive adhesive in addition to the above-mentioned additives as long as the effect of the present invention is not impaired. You may be doing it.
Examples of such additives for adhesives include antioxidants, softeners (plasticizers), rust preventives, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers and the like.
These adhesive additives may be used alone or in combination of two or more.

When these additives for adhesives are contained, the content of each additive for adhesives is preferably 0.0001 to 20 parts by mass, more preferably 0.001 with respect to 100 parts by mass of the adhesive resin. It is 10 parts by mass.

When the pressure-sensitive adhesive sheet (I) of the second aspect described above is used as the pressure-sensitive adhesive laminate 2 shown in FIG. 3, the first pressure-sensitive adhesive layer (X11), which is a heat-expandable pressure-sensitive adhesive layer, is further increased. It is formed from a heat-expandable pressure-sensitive adhesive composition (x11) containing heat-expandable particles.
The thermally expandable particles are as described above.
The content of the heat-expandable particles is preferably relative to the total amount (100% by mass) of the active ingredient of the heat-expandable pressure-sensitive adhesive composition (x11) or the total mass (100% by mass) of the heat-expandable pressure-sensitive adhesive layer. Is 1 to 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, still more preferably 5 to 40% by mass.

On the other hand, when the pressure-sensitive adhesive layer (X1) is a non-heat-expandable pressure-sensitive adhesive layer, the content of the heat-expandable particles in the non-heat-expandable pressure-sensitive adhesive composition which is a material for forming the non-heat-expandable pressure-sensitive adhesive layer is The smaller the amount, the more preferable.
The content of the heat-expandable particles is preferably relative to the total amount (100% by mass) of the active ingredient of the non-heat-expandable pressure-sensitive adhesive composition or the total mass (100% by mass) of the non-heat-expandable pressure-sensitive adhesive layer. It is less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass.

A pressure-sensitive adhesive sheet (I) having a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), which are non-thermally expandable pressure-sensitive adhesive layers, as shown in the pressure-sensitive adhesive laminates 1c and 1d shown in FIG. when using a), at 23 ° C., the storage shear modulus G of the first pressure-sensitive adhesive layer is a non-heat-expandable pressure-sensitive adhesive layer (X11) '(23) is preferably not more than 1.0 × ¹⁰ 8 Pa, more It is preferably 5.0 × 10 ⁷ Pa or less, and more preferably 1.0 × 10 ⁷ Pa or less.
If non-heat-expandable pressure-sensitive adhesive layer a first pressure-sensitive adhesive layer is (X11) of the storage shear modulus G '(23) is less than 1.0 × 10 8 ^Pa, for example, adhesive laminated body shown in FIG. 2 When the configurations are 1c and 1d, the heat-expandable particles in the heat-expandable base material layer (Y1-1) due to the heat treatment for separation come into contact with the resin film-forming sheet (II). Unevenness is likely to be formed on the surface of the first pressure-sensitive adhesive layer (X11). As a result, it is possible to obtain an adhesive laminate that can be easily separated at the interface P between the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) with a slight force. ..
The storage shear elastic modulus G'(23) of the first pressure-sensitive adhesive layer (X11), which is a non-thermally expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5. It is 0.0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

[Structure of resin film forming sheet (II)]
In the adhesive laminate of the present invention, the resin film-forming sheet (II) has a curable resin layer (Z2) on one surface side of the base material (Y2), and the other surface of the base material (Y2). The adhesive sheet (I) is directly laminated on the side.
Further, in the adhesive laminate according to one aspect of the present invention, the resin film forming sheet (II) has an adhesive layer (X2) between the base material (Y2) and the curable resin layer (Z2). You may be doing it.

Here, from the viewpoint that the base material (Y2) of the resin film forming sheet (II) and the adhesive sheet (I) can be easily separated at the interface P with a slight force, the base material (Y2) is , A non-thermally expandable base material is preferable.
The volume change rate (%) of the base material (Y2) calculated from the above formula is less than 5%, but preferably less than 2%, more preferably less than 1%, still more preferably less than 0.1%. , More preferably less than 0.01%.
Hereinafter, the base material (Y2), the curable resin layer (Z2), and the pressure-sensitive adhesive layer (X2) will be described.

<Base material (Y2)>
Examples of the material for forming the base material (Y2) include the same materials as those for forming the non-thermally expandable base material layer (Y1-2) described above.
The base material (Y2) preferably contains a resin, and it is more preferable that a resin layer containing the resin is formed at least on the surface of the base material (Y2) on the side where the adhesive sheet (I) is laminated. It is more preferable that the base material (Y2) is a resin film or a resin sheet.
Further, from the viewpoint of making it possible to easily separate all at once at the interface P after the heat treatment for separation, the surface on the side where the adhesive sheet (I) of the base material (Y2) is laminated is subjected to a peeling treatment. It is preferably a flat surface.

Further, from the viewpoint of making it easy to prevent misalignment when the object to be processed such as a semiconductor chip is attached to the curable resin layer (Z2), and when the object to be processed is attached to the curable resin during heating. from the viewpoint of those liable to prevent narrowing excessive sink to the layer (Z2), as the storage modulus E at 23 ° C. of the substrate (Y2) '(23), is 1.0 × ¹⁰ 6 Pa or more Is preferable.

The base material (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range, but from the above viewpoint, the content of the thermally expandable particles in the base material (Y2) is , The smaller the number, the better.
The content of the heat-expandable particles in the base material (Y2) is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than the total mass (100% by mass) of the base material (Y2). It is less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.

The thickness of the base material (Y2) is preferably 10 to 1000 μm, more preferably 20 to 700 μm, still more preferably 25 to 500 μm, and even more preferably 30 to 300 μm.

<Curable resin layer (Z2)>
The curable resin layer (Z2) may be formed from a composition that can be cured to form a cured resin film, but the curable composition (B) containing the polymer component (A) and the curable component (B). It is preferably a layer formed from z).
The curable composition (z) may further contain one or more selected from the colorant (C), the coupling agent (D), and the inorganic filler (E).
Further, the curable composition (z) further contains a cross-linking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a gettering agent, and a chain transfer agent as long as the effects of the present invention are not impaired. Additives such as agents may also be included.
Hereinafter, the components (A) to (F) contained in the curable composition (z), which is a material for forming the curable resin layer (Z2), will be described.

(Polymer component (A))
The polymer component (A) contained in the curable composition (z) means a compound having a mass average molecular weight of 20,000 or more and having at least one repeating unit. By containing the polymer component (A) in the curable resin layer (Z2), the curable resin layer (Z2) is mainly imparted with flexibility and film-forming property, and the sheet property retention property is improved. can do.
The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3 million, more preferably 50,000 to 2 million, still more preferably 100,000 to 1.5 million. More preferably, it is 200,000 to 1,000,000.

The content of the component (A) is preferably 5 to 5 with respect to the total amount (100% by mass) of the active ingredient of the curable composition (z) or the total mass (100% by mass) of the curable resin layer (Z2). It is 50% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 30% by mass.
The polymer component (A) may be used alone or in combination of two or more.
Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber-based polymers and the like.
In the present specification, the acrylic polymer (A1) having an epoxy group and the phenoxy resin having an epoxy group have thermosetting properties, but fall under the above-mentioned "polymer component". If so, these are included in the concept of the polymer component (A) rather than the curable component (B).

Among these, the polymer component (A) preferably contains an acrylic polymer (A1).
The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100% by mass, more preferably 70 to 70 to the total amount (100% by mass) of the polymer component (A). It is 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

(Acrylic polymer (A1))
The mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3 million, more preferably 100,000 from the viewpoint of imparting flexibility and film-forming property to the curable resin layer (Z2). It is ~ 1.5 million, more preferably 150,000 to 1.2 million, and even more preferably 250,000 to 1 million.

The glass transition temperature (Tg) of the acrylic polymer (A1) is determined from the viewpoint of the adhesiveness of the curable resin layer (Z2) to the adherend, and the resin produced by using the resin film forming sheet (II). From the viewpoint of improving the reliability of the processed object with a film, the temperature is preferably -60 to 50 ° C, more preferably -50 to 30 ° C, further preferably -40 to 10 ° C, still more preferably -5 to 5 ° C. is there.

Examples of the acrylic polymer (A1) include polymers containing an alkyl (meth) acrylate as a main component, and specifically, an alkyl (meth) acrylate (a1') having an alkyl group having 1 to 18 carbon atoms. An acrylic polymer containing a structural unit (a1) derived from (hereinafter, also referred to as "monomer (a1')") is preferable, and a functional group-containing monomer (a2') (hereinafter, "monomer (a1')" is preferable together with the structural unit (a1). An acrylic copolymer containing a structural unit (a2) derived from "a2')" is more preferable.
The component (A1) may be used alone or in combination of two or more.
When the component (A1) is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

The number of carbon atoms of the alkyl group contained in the monomer (a1') is preferably 1 to 18, more preferably 1 to 12, from the viewpoint of imparting flexibility and film-forming property to the curable resin layer (Z2). More preferably, it is 1 to 8. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
Examples of the monomer (a1') include the same monomers as the above-mentioned monomer (p1').
These monomers (a1') may be used alone or in combination of two or more.

From the viewpoint of improving the reliability of the processed object with a resin film produced by using the resin film forming sheet (II), the monomer (a1') is an alkyl (meth) having an alkyl group having 1 to 3 carbon atoms. ) It is preferable to contain an acrylate, and it is more preferable to contain a methyl (meth) acrylate.
From the above viewpoint, the content of the structural unit (a11) derived from the alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is based on the total structural unit (100% by mass) of the acrylic polymer (A1). It is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, and further preferably 10 to 80% by mass.

Further, from the viewpoint of increasing the gloss value of the resin film of the processed object having a resin film produced by using the resin film forming sheet (II) and improving the laser marking suitability, the monomer (a1') is carbon. It is preferable to contain an alkyl (meth) acrylate having an alkyl group of several 4 or more, more preferably to contain an alkyl (meth) acrylate having an alkyl group having 4 to 6 carbon atoms, and preferably to contain a butyl (meth) acrylate. More preferred.
From the above viewpoint, the content of the structural unit (a12) derived from the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms (preferably 4 to 6, more preferably 4) is the acrylic polymer (A1). It is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and further preferably 10 to 60% by mass with respect to all the constituent units (100% by mass).

The content of the structural unit (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, and further preferably 55 with respect to the total structural unit (100% by mass) of the acrylic polymer (A1). It is ~ 90% by mass, more preferably 60 to 90% by mass.

Examples of the monomer (a2') include the same ones as the above-mentioned monomer (p2'), but one or more selected from a hydroxy group-containing monomer and an epoxy group-containing monomer are preferable.
The monomer (a2') may be used alone or in combination of two or more.

Examples of the hydroxy group-containing monomer include the same as the above-mentioned hydroxyl group-containing compound, and hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

Examples of the epoxy-containing monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate. Epoxy group-containing (meth) acrylates such as glycidyl crotonate, allyl glycidyl ether and the like.
Among these, epoxy group-containing (meth) acrylate is preferable, and glycidyl (meth) acrylate is more preferable.

The content of the structural unit (a2) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, still more preferably 5 to 45% by mass, based on the total structural unit (100% by mass) of the acrylic polymer (A1). It is 10 to 40% by mass, more preferably 10 to 30% by mass.

The acrylic polymer (A1) may have a structural unit derived from a monomer other than the above-mentioned structural units (a1) and (a2) as long as the effect of the present invention is not impaired.
Examples of other monomers include vinyl acetate, styrene, ethylene, α-olefin and the like.

<Curable component (B)>
The curable component (B) plays a role of curing the curable resin layer (Z2) to form a hard resin film, and is a compound having a mass average molecular weight of less than 20,000.
It is preferable to use a thermosetting component (B1) and / or an energy ray-curable component (B2) as the curable component (B), and a viewpoint of suppressing coloring of the resin film formed from the curable resin layer (Z2) It is more preferable to use the thermosetting component (B1) from the viewpoint of sufficiently advancing the curing reaction and reducing the cost.

The thermosetting component (B1) preferably contains at least a compound having a functional group that reacts by heating.
Further, the energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts by irradiation with energy rays, and is polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams.
Curing is realized by reacting the functional groups of these curable components with each other to form a three-dimensional network structure.

When the thermosetting component (B1) is used, when the curable resin layer (Z2) to be formed is cured before being separated at the interface P, it is heated at a temperature lower than the thermal expansion start temperature (t). And cure.
When the energy ray-curable component (B2) is used, the curable resin layer (Z2) to be formed is subjected to energy irradiation separately from the heat treatment to be cured.

When the mass average molecular weight (Mw) of the curable component (B) is used in combination with the component (A), the viscosity of the composition for forming the curable resin layer (Z2) is suppressed and the handleability is improved. It is preferably less than 20,000, more preferably 10,000 or less, still more preferably 100 to 10,000, from the viewpoint of allowing the mixture to grow.

(Thermosetting component (B1))
As the thermosetting component (B1), an epoxy-based thermosetting component is preferable.
As the epoxy-based thermosetting component, it is preferable to use a combination of an epoxy compound (B11), which is a compound having an epoxy group, and a thermosetting agent (B12).

Examples of the epoxy compound (B11) include polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, and bisphenol A type epoxy resin. , Bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, and the like, which have bifunctionality or more in the molecule and have a mass average molecular weight of less than 20,000.
These epoxy compounds (B11) may be used alone or in combination of two or more.

The content of the epoxy compound (B11) is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, still more preferably 10 to 150 parts by mass, still more preferably, with respect to 100 parts by mass of the component (A). Is 20 to 120 parts by mass.

(Thermosetting agent (B12))
The thermosetting agent (B12) functions as a curing agent for the epoxy compound (B11).
As the thermosetting agent, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule is preferable.
Examples of the functional group include phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, acid anhydrides and the like. Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable, a phenolic hydroxyl group or an amino group is more preferable, and an amino group is further preferable.

Examples of the phenol-based thermocuring agent having a phenol group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, zylock-type phenol resins, and aralkylphenol resins.
Examples of the amine-based thermosetting agent having an amino group include dicyandiamide (DICY) and the like.
These thermosetting agents (B12) may be used alone or in combination of two or more.

The content of the thermosetting agent (B12) is preferably 0.1 to 500 parts by mass, and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the epoxy compound (B11).

(Curing accelerator (B13))
A curing accelerator (B13) may be used to adjust the rate of thermosetting of the curable resin layer (Z2). The curing accelerator (B13) is preferably used in combination with the epoxy compound (B11) as a thermosetting component (B1).

Examples of the curing accelerator (B13) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, and the like. Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine and the like. Organic phosphines; tetraphenylborone salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate can be mentioned.
These curing accelerators (B13) may be used alone or in combination of two or more.

The content of the curing accelerator (B13) is determined from the viewpoint of improving the adhesiveness of the curable resin layer (Z2) and the reliability of the processed object with a resin film produced by using the resin film forming sheet (II). From the viewpoint of improving the above, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, based on 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). It is preferably 0.3 to 4 parts by mass.

(Energy ray curable component (B2))
As the energy ray-curable component (B2), a compound (B21) having a functional group that reacts by irradiation with energy rays may be used alone, or a photopolymerization initiator (B22) may be combined with the compound (B21). It is preferable to use it.

(Compound having a functional group that reacts by irradiation with energy rays (B21))
Examples of the compound (B21) having a functional group that reacts by irradiation with energy rays (hereinafter, also referred to as “energy ray-reactive compound (B21)”) include trimethylpropantriacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. , Dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, oligoester acrylate, urethane acrylate-based oligomer, epoxy acrylate, polyether acrylate, itacon Examples thereof include acid oligomers.
These energy ray-reactive compounds (B21) may be used alone or in combination of two or more.
The mass average molecular weight (Mw) of the energy ray-reactive compound (B21) is preferably 100 to 30,000, more preferably 300 to 10,000.

The content of the energy ray-reactive compound (B21) is preferably 1 to 1500 parts by mass, and more preferably 3 to 1200 parts by mass with respect to 100 parts by mass of the component (A).

(Photopolymerization Initiator (B22))
When used in combination with the above-mentioned energy ray-reactive compound (B21) and a photopolymerization initiator (B22), the polymerization curing time can be shortened and the curable resin layer (Z2) can be cured even if the amount of light irradiation is small. Can be advanced.
Examples of the photopolymerization initiator (B22) include the same as those blended in the solvent-free resin composition (y1) described above.
The content of the photopolymerization initiator (B22) is preferably 0.1 with respect to 100 parts by mass of the energy ray-reactive compound (B21) from the viewpoint of sufficiently advancing the curing reaction and suppressing the formation of residues. It is 10 parts by mass, more preferably 1 to 5 parts by mass.

The content of the component (B) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and further preferably 10 to 30 with respect to the total amount (100% by mass) of the curable resin layer (Z2). It is by mass, more preferably 12 to 25% by mass.
The content of the component (B) includes the thermosetting component (B1) containing the above-mentioned epoxy compound (B11), thermosetting agent (B12), and curing accelerator (B13), and energy ray reactivity. It is the total content of the energy ray curable component (B2) containing the compound (B21) and the photopolymerization initiator (B22).

<Colorant (C)>
The curable resin layer (Z2) preferably further contains a colorant (C).
By containing the colorant (C) in the curable resin layer (Z2), a processed object having a resin film formed from the curable resin layer (Z2), for example, a semiconductor chip having a resin film is incorporated into an apparatus. At that time, it is possible to prevent malfunction of the semiconductor chip by shielding infrared rays and the like generated from surrounding devices.

As the colorant (C), organic or inorganic pigments and dyes can be used.
As the dye, for example, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, and a cationic dye can be used.
The pigment is not particularly limited, and can be appropriately selected from known pigments and used.
Among these, black pigments are preferable from the viewpoint of good shielding of electromagnetic waves and infrared rays and further improving the distinguishability by the laser marking method.
Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon and the like, but carbon black is preferable from the viewpoint of improving the reliability of the semiconductor chip.
In addition, these colorants (C) may be used alone or in combination of 2 or more types.

The content of the component (C) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, still more preferably, based on the total amount (100% by mass) of the curable resin layer (Z2). Is 1.0 to 15% by mass, more preferably 1.2 to 5% by mass.

<Coupling agent (D)>
The curable resin layer (Z2) preferably further contains a coupling agent (D).
By containing the coupling agent (D), the polymer component in the curable resin layer (Z2) is bonded to the surface of the object to be processed such as a semiconductor chip or the surface of the filler to improve the adhesiveness and cohesiveness. be able to. Further, the water resistance can be improved without impairing the heat resistance of the resin film formed from the curable resin layer (Z2).

As the coupling agent (D), a compound that reacts with the functional groups of the component (A) and the component (B) is preferable, and a silane coupling agent is more preferable.
Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ- (methacryloxy). Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfan, methyltri Examples thereof include methoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazolesilane.
These (D) coupling agents may be used alone or in combination of two or more.

As the coupling agent (D), an oligomer type coupling agent is preferable.
The molecular weight of the coupling agent (D) including the oligomer-type coupling agent is preferably 100 to 15,000, more preferably 150 to 10000, more preferably 200 to 5000, still more preferably 250 to 3000, and even more preferably. Is 350-2000.

The content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, still more preferably, based on the total amount (100% by mass) of the curable resin layer (Z2). Is 0.10 to 4% by mass, more preferably 0.15 to 2% by mass.

<Inorganic filler (E)>
The curable resin layer (Z2) preferably further contains an inorganic filler (E).
By including the inorganic filler (E), it is possible to adjust the thermal expansion coefficient of the cured resin film of the curable resin layer (Z2) within an appropriate range, and it is possible to adjust the thermal expansion coefficient to an appropriate range for a processed object such as a semiconductor chip. The thermal expansion coefficient of the cured resin film can be optimized, and a product containing the resin film formed by the curable resin layer (Z2) and the object to be processed, for example, when the object to be processed is a semiconductor chip. The reliability of the semiconductor chip can be improved. It is also possible to reduce the hygroscopicity of the resin film after curing.

The inorganic filler (E) may be a non-thermally expandable material, for example, powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride and the like, which are spherically formed. Examples thereof include non-thermally expanding particles such as beads, single crystal fibers and glass fibers.
These inorganic fillers (E) may be used alone or in combination of two or more.
Among these, silica or alumina is preferable.

The average particle size of the inorganic filler (E) is preferably 0 from the viewpoint of improving the gloss value of the resin film of the processed object with the resin film produced by using the resin film forming sheet (II). It is 3 to 50 μm, more preferably 0.5 to 30 μm, and even more preferably 0.7 to 10 μm.

The content of the component (E) is preferably 25 to 80% by mass, more preferably 30 to 70% by mass, still more preferably 40 to 65, based on the total amount (100% by mass) of the curable resin layer (Z2). It is by mass, more preferably 45 to 60% by mass.

<Adhesive layer (X2)>
The pressure-sensitive adhesive layer (X2) contained in the resin film-forming sheet (II) can be formed by using the above-mentioned pressure-sensitive adhesive composition (x1), and suitable components and a suitable range of the content of each component are also available. It is the same as the pressure-sensitive adhesive composition (x1).

After the curable resin layer (Z2) is cured to form a cured resin film, the layers other than the curable resin layer (Z2) of the resin film forming sheet (II) are removed.
Therefore, the pressure-sensitive adhesive layer (X2) has a good interlayer adhesion with the curable resin layer (Z2) before curing, but after the curable resin layer (Z2) is cured to form a cured resin film. Is preferably adjusted so that it can be easily peeled off.
From the above viewpoint, the pressure-sensitive adhesive composition, which is a material for forming the pressure-sensitive adhesive layer (X2), preferably contains, as the pressure-sensitive adhesive, an energy ray-curable pressure-sensitive adhesive resin in which a polymerizable functional group is introduced into the side chain. ..

The thickness of the pressure-sensitive adhesive layer (X2) is preferably 1 to 60 μm, more preferably 2 to 50 μm, still more preferably 3 to 40 μm, and even more preferably 5 to 30 μm.

<Release material>
In the adhesive laminate of one aspect of the present invention, a release material may be further laminated on the surfaces of the pressure-sensitive adhesive layer (X1) and the curable resin layer (X2) to be attached to the adherend.
Examples of the release material include a release sheet that has been subjected to double-sided release treatment, a release sheet that has undergone single-sided release treatment, and the like, and a release agent coated on a base material for the release material.

Examples of the base material for the release material include papers such as high-quality paper, glassin paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin, and olefins such as polypropylene resin and polyethylene resin. Plastic films such as resin films; etc. may be mentioned.

Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

The thickness of the release material is not particularly limited, but is preferably 10 to 200 μm, more preferably 25 to 170 μm, and even more preferably 35 to 80 μm.

[Manufacturing method of processed object with resin film]
In the adhesive laminate of the present invention, the object to be processed can be fixed to the support to perform a predetermined process, and after the process, the adhesive laminate can be easily separated from the support collectively with a slight force. Moreover, after separation, a processed object with a resin film capable of forming a cured resin film can be obtained.
Therefore, by using the adhesive laminate of the present invention, the work of attaching the adhesive sheet to the object to be processed in order to fix the object to be processed to the support before processing and the work of removing the adhesive sheet from the object to be processed after processing. The work of attaching the resin film forming sheet can be performed at once, and an improvement in productivity can be expected.

As a more specific method for producing a processed object with a resin film, a method having the following steps (α-1) to (α-3) can be mentioned.
Step (α-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. Step / process (α-2) of placing or affixing the object to be processed on the surface of Z2): Step / process (α-3) of performing a predetermined process on the object to be processed: start of thermal expansion of thermally expandable particles A step of separating the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) at the interface P by heating at a temperature (t) or higher to obtain a processed object with a resin film.

Further, if necessary, it is preferable to have the following step (α-2') after the step (α-2) and before the step (α-3).
-Step (α-2'): A step of curing the curable resin layer (Z2) to form a cured resin film.
Hereinafter, each step described above will be described with reference to FIG. 4 as appropriate.

<Process (α-1)>
In the step (α-1), the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. This is a step of placing or affixing the object to be processed on the surface of Z2).
FIG. 4A is a schematic cross-sectional view showing a state in which an object to be processed is fixed to a support via the adhesive laminate 1a of the first aspect of the present invention shown in FIG. 1A.
In the step (α-1), as shown in FIG. 4A, the object to be processed 60 is fixed to the support 50 via the adhesive laminate 1a of the first aspect of the present invention, and the support The adhesive laminate and the processing inspection object are laminated in this order.
Note that FIG. 4 shows an example in which the adhesive laminate 1a shown in FIG. 1A is used, but similarly, when the adhesive laminate 1a of the present invention having another configuration is used, the same applies. The support, the adhesive laminate, and the processing inspection object are laminated in this order.

Examples of the object to be processed to be attached to the adhesive laminate include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panel substrates.

The support is used in the step (α-2) to fix the object to be processed and improve the accuracy of processing.
The support is preferably attached to the entire surface of the adhesive surface of the adhesive layer (X1) of the adhesive laminate.
Therefore, the support is preferably plate-shaped. Further, the area of the adhesive surface of the pressure-sensitive adhesive layer (X1) and the surface of the support on the side to be attached is preferably equal to or larger than the area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1), as shown in FIG.

The material constituting the support is appropriately selected in consideration of required characteristics such as mechanical strength and heat resistance according to the type of the object to be processed and the processing performed in the process (α-2). Will be done.
Specific materials constituting the support include metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, and polyimide resins. Resin materials such as polyamideimide resin; composite materials such as glass epoxy resin are mentioned, and among these, SUS, glass, silicon wafer and the like are preferable.
Examples of engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like.
Examples of super engineering plastics include polyphenylene sulfide (PPS), polyethersulfone (PES), and polyetheretherketone (PEEK).

The thickness of the support is appropriately selected in consideration of the type of processing in the next step and the like, but is preferably 20 μm or more and 50 mm or less, and more preferably 60 μm or more and 20 mm or less.

The temperature condition in the step (α-1) may be less than the expansion start temperature (t) of the thermally expandable particles, but in an environment of 0 to 80 ° C. (expansion start temperature (t) is 60 to 80). In the case of ° C., it is preferable to carry out the operation in an environment of less than the expansion start temperature (t).

<Process (α-2)>
The step (α-2) is a step of performing a predetermined process on the processing object attached to the curable resin layer (Z2) of the adhesive laminate of the present invention in the step (α-1).
The processing performed in the step (α-2) includes, for example, sealing processing of an object using resin, grinding processing of the object, dicing (individualization) processing, circuit formation processing, etching processing, plating processing, and sputtering. Examples include treatment, vapor deposition treatment, and laminating treatment using a separately prepared adhesive sheet.
In this step (α-2), two or more of these processes may be used in combination.

As the temperature condition in the step (α-2), it is preferable that the temperature is set in a temperature environment lower than the expansion start temperature (t) of the thermally expandable particles.
Further, in the step (α-2), the curable resin layer (Z2) may be cured to form a cured resin film in parallel with the execution of the above processing. For example, when the processing performed in this step involves heating, the curable resin layer (Z2) can be cured by the heat to form a cured resin film.

If the curable resin layer (Z2) is not cured during the processing of the step (α-2), if necessary, after the step (α-2) and before the step (α-3), As a step (α-2'), a step of curing the curable resin layer (Z2) to form a cured resin film may be performed.
When the curable resin layer (Z2) is cured by heating in the step (α-2'), the temperature condition is that it is performed in a temperature environment lower than the expansion start temperature (t) of the thermally expandable particles. preferable.

<Process (α-3)>
In the step (α-3), the interface between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) is formed by heating the heat-expandable particles above the thermal expansion start temperature (t). This is a step of separating with P to obtain a processed object with a resin film.
FIG. 4B is a schematic cross-sectional view showing a state of being separated at the interface P by heat treatment.
FIG. 4B shows a state in which the processing inspection object is separated in a laminated state on the resin film forming sheet (II) by the heat treatment.

In the step (α-3), the “expansion start temperature (t) or higher” during the heat treatment is “expansion start temperature (t) + 10 ° C.” or higher and “expansion start temperature (t) + 60 ° C.” or lower. It is preferably present, and more preferably "expansion start temperature (t) + 15 ° C." or more and "expansion start temperature (t) + 40 ° C." or less.

Here, it is preferable that the heat source for the heat treatment is provided on the support side. It can be easily separated at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the base material (Y2) of the resin film-forming sheet (II).

In this way, after separation at the interface P, the processing object with the resin film on which the resin film forming sheet (II) is attached to the processing object can be obtained.
If the curable resin layer (Z2) is uncured even after separation, the curable resin layer (Z2) can be cured to form a cured resin film.
After forming the cured resin film, the resin film forming sheet (II) other than the curable resin layer (Z2) can be removed to obtain a processed object with a cured resin film.

[Manufacturing method of cured encapsulant with cured resin film]
By using the adhesive laminate of the present invention, productivity can be improved and a cured encapsulant with a cured resin film can also be produced.
More specific methods for producing a cured encapsulant with a cured resin film include production methods having the following steps (β-1) to (β-3).
Step (β-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. Step / Step (β-2) of placing a semiconductor chip on Z2): The semiconductor chip is coated with a sealing material, the sealing material is cured, and the semiconductor chip is sealed. Step / Step (β-3) of curing the body and the curable resin layer (Z2) to form a curable resin film: Adhesion by heating the thermosetting particles at a thermal expansion start temperature (t) or higher. A step of separating the sheet (I) and the base material (Y2) of the resin film forming sheet (II) at the interface P to obtain a cured encapsulant with a cured resin film.

<Step (β-1)>
In the step (β-1), the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. This is a step of mounting a semiconductor chip on Z2).
The support used in the step (β-1) is as described above.
Further, as the semiconductor chip, a conventionally known one can be used, and an integrated circuit composed of circuit elements such as a transistor, a resistor, and a capacitor is formed on the circuit surface thereof.
The semiconductor chip is preferably placed so that the back surface opposite to the circuit surface is covered with the surface of the curable resin layer (Z2) of the resin film forming sheet (II). In this case, the circuit surface of the semiconductor chip is exposed after mounting.
A known device such as a flip chip bonder or a die bonder can be used for mounting the semiconductor chip.
The layout of the arrangement of the semiconductor chips, the number of arrangements, and the like may be appropriately determined according to the form of the target package, the number of production, and the like.

Here, like FOWLP, FOPLP, etc., the semiconductor chip is covered with a sealing material in a region larger than the chip size to form a rewiring layer not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material. It is preferable that it is applied to the package to be used.
Therefore, the semiconductor chip is placed on a part of the surface of the curable resin layer (Z2), and a plurality of semiconductor chips are placed on the surface in a state of being aligned at a certain interval. It is more preferable that the plurality of semiconductor chip CPs are placed on the surface in a state of being arranged in a matrix of a plurality of rows and a plurality of columns at regular intervals.
The distance between the semiconductor chips may be appropriately determined according to the form of the target package and the like.

<Step (β-2)>
In the step (β-2), the semiconductor chip is coated with a sealing material (hereinafter, also referred to as “coating treatment”), the sealing material is cured (hereinafter, also referred to as “curing treatment”), and the semiconductor is described. This is a step of forming a cured resin film by curing a cured sealed body in which chips are sealed and a curable resin layer (Z2).
In the coating treatment of the step (β-2), first, the semiconductor chip and at least the peripheral portion of the surface of the curable resin layer (Z2) of the semiconductor chip are coated with a sealing material. The encapsulant covers the entire exposed surface of the semiconductor chip and is also filled in the gaps between the plurality of semiconductor chips.

The encapsulant has a function of protecting the semiconductor chip and its associated elements from the external environment.
As the sealing material, any material can be appropriately selected and used from those used as semiconductor sealing materials, for example, a sealing material containing a thermosetting resin or an energy ray curable resin. Examples thereof include a sealing material containing.
Further, the encapsulant may be a solid such as granules or sheets at room temperature or a liquid in the form of a composition, but from the viewpoint of workability, the encapsulant may be a sheet. Is preferable.

As a method of coating the semiconductor chip and its peripheral portion by using the encapsulant, the method is appropriately selected and applied according to the type of the encapsulant from the methods conventionally applied to the semiconductor encapsulation step. For example, a roll laminating method, a vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a transfer molding method, a compression molding molding method, or the like can be applied.

Then, after performing the coating treatment, the sealing material is cured to obtain a cured sealing body in which the semiconductor chip is sealed by the cured sealing material.
The coating treatment and the curing treatment in the step (β-2) are preferably performed under temperature conditions lower than the expansion start temperature (t) of the heat-expandable particles.
Further, the coating step and the curing step may be carried out separately, but when the sealing material is heated in the coating step, the sealing material is cured as it is by the heating, and the coating step and the curing step are performed. May be carried out at the same time.

In this step (β-2), in the curing treatment for curing the sealing material, the curable resin layer (Z2) is also cured to form a cured resin film.
When the curable resin layer (Z2) is thermosetting, the curable resin layer (Z2) can be cured together with the encapsulant by heating by a curing treatment for curing the encapsulant.
When the curable resin layer (Z2) is energy ray curable, the curable resin layer (Z2) is cured by separately irradiating the curable resin layer (Z2) with energy rays to cure the curable resin layer (Z2). A resin film can be formed.

<Step (β-3)>
In the step (β-3), the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are heated by heating the heat-expandable particles above the thermal expansion start temperature (t). This is a step of separating at the interface P to obtain a cured encapsulant with a cured resin film.
By heating at the thermal expansion start temperature (t) or higher, the thermal expansion particles expand, and the surface of the adhesive sheet (I) on the base material (Y2) side of the resin film forming sheet (II) becomes uneven. As a result, they can be easily separated at the interface P with a slight force.
The temperature conditions for the heat treatment in the step (β-3) are as described above.

After separation at the interface P, the layer of the resin film forming sheet (II) other than the curable resin layer (Z2) is removed to obtain a cured encapsulant with a cured resin film.
After that, the cured sealant is ground until the circuit surface of the semiconductor chip is exposed, and the circuit surface is rewired or an external electrode pad is formed to connect the external electrode pad and the external terminal electrode. And so on. Further, after the external terminal electrode is connected to the cured sealant, it can be separated into individual pieces to manufacture a semiconductor device.

The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples. The physical property values in the following production examples and examples are values measured by the following methods.

<Mass average molecular weight (Mw)>
It was measured under the following conditions using a gel permeation chromatograph device (manufactured by Tosoh Corporation, product name "HLC-8020"), and the value measured in terms of standard polystyrene was used.
(Measurement condition)
-Column: "TSK guard volume HXL-L""TSK gel G2500HXL""TSK gel G2000HXL""TSK gel G1000HXL" (all manufactured by Tosoh Corporation) are connected in sequence.-Column temperature: 40 ° C.
-Development solvent: tetrahydrofuran-Flow velocity: 1.0 mL / min

<Measurement of thickness of each layer>
The measurement was performed using a constant pressure thickness measuring instrument manufactured by Teclock Co., Ltd. (model number: "PG-02J", standard: JIS K6783, Z1702, Z1709).

<Average particle size of thermally expandable particles (D ₅₀ ), 90% particle size (D ₉₀ )>
Using a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name “Mastersizer 3000”), the particle distribution of the thermally expandable particles before expansion at 23 ° C. was measured.
Then, the particle diameters corresponding to the cumulative volume frequencies of 50% and 90% calculated from the smaller particle diameter of the particle distribution are set to "average particle diameter of thermally expandable fine particles (D ₅₀ )" and "thermally expandable particles", respectively. 90% particle size (D ₉₀ ) ”.

<Storing elastic modulus E'of the heat-expandable base material layer (Y1-1)>
The formed heat-expandable base material layer (Y1-1) had a size of 5 mm in length × 30 mm in width × 200 μm in thickness, and the one from which the release material was removed was used as a test sample.
Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), test start temperature 0 ° C, test end temperature 300 ° C, temperature rise rate 3 ° C / min, frequency 1 Hz, amplitude 20 μm The storage elastic modulus E'of the test sample at a predetermined temperature was measured under the conditions of.

<Storage shear modulus G'of the adhesive layers (X11) and (X12)>
The formed adhesive layers (X11) and (X12) were cut into a circle having a diameter of 8 mm, the release material was removed, and the adhesive layers (X12) were overlapped to obtain a thickness of 3 mm as a test sample.
Torsional shearing method using a viscoelasticity measuring device (manufactured by Antonio Par, device name "MCR300") under the conditions of test start temperature 0 ° C, test end temperature 300 ° C, temperature rise rate 3 ° C / min, and frequency 1 Hz. The stored shear viscoelasticity G'of the test sample at a predetermined temperature was measured.

<Probe tack value>
A test sample was prepared by cutting a base material to be measured into a square having a side of 10 mm and then allowing it to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity).
In an environment of 23 ° C. and 50% RH (relative humidity), use a tacking tester (manufactured by Nippon Special Instruments Co., Ltd., product name "NTS-4800") to determine the probe tack value on the surface of the test sample. Measured according to Z0237: 1991.
Specifically, a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample for 1 second with a contact load of 0.98 N / cm ² , and then the probe is brought into contact with the surface of the test sample at a speed of 10 mm / sec. The force required to separate from the surface was measured, and the obtained value was used as the probe tack value of the test sample.

<Measurement of adhesive strength of adhesive layer before heat treatment for separation>
A 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) was laminated on the adhesive surface of the adhesive layer formed on the release film to obtain an adhesive sheet with a base material.
Then, the release film is removed, and the adhesive surface of the exposed adhesive layer is attached to a stainless steel plate (SUS304 No. 360 polishing) as an adherend, and in an environment of 23 ° C. and 50% RH (relative humidity). After standing for 24 hours, the adhesive strength at 23 ° C. was measured at a tensile speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000 under the same environment.

<Measurement of adhesive strength of curable resin layer (Z2)>
The surface of the exposed curable resin layer (Z2) is attached to a stainless steel plate (SUS304 No. 360 polished) as an adherend, and is allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity). After placement, the adhesive strength at 23 ° C. was measured at a tensile speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000 under the same environment.

Production Example 1 (Synthesis of Urethane Prepolymer)
In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate is used as an equivalent ratio of the hydroxyl group of the carbonate-type diol to the isocyanate group of the isophorone diisocyanate with respect to 100 parts by mass (solid content ratio) of the carbonate-type diol having a mass average molecular weight of 1,000. Was compounded so as to be 1/1, and 160 parts by mass of toluene was further added, and the mixture was reacted at 80 ° C. for 6 hours or more with stirring under a nitrogen atmosphere until the isocyanate group concentration reached the theoretical amount.
Then, a solution obtained by diluting 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by mass of toluene was added, and the temperature was further increased at 80 ° C. until the isocyanate groups at both ends disappeared. The reaction was carried out for 6 hours to obtain a urethane prepolymer having a mass average molecular weight of 29000.

Production Example 2 (Synthesis of Acrylic Urethane Resin)
In a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solid content ratio) of the urethane prepolymer obtained in Production Example 1, 117 parts by mass (solid content ratio) of methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (2-HEMA). ) 5.1 parts by mass (solid content ratio), 1.1 parts by mass of 1-thioglycerol (solid content ratio), and 50 parts by mass of toluene were added, and the temperature was raised to 105 ° C. with stirring.
Then, in the reaction vessel, a solution obtained by further diluting 2.2 parts by mass (solid content ratio) of the radical initiator (manufactured by Japan Finechem Co., Ltd., product name "ABN-E") with 210 parts by mass of toluene is brought to 105 ° C. The mixture was added dropwise over 4 hours while being maintained.
After completion of the dropping, the reaction was carried out at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin having a mass average molecular weight of 105,000.

Production Example 3 (Preparation of curable composition)
Each component of the type and blending amount (all "active ingredient ratio") shown below is blended, further diluted with methyl ethyl ketone, and uniformly stirred to have a curable composition having a solid content concentration (active ingredient concentration) of 61% by mass. A solution of the substance was prepared.
Acrylic polymer: 28 parts by mass of compounding amount Acrylic weight obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate. Combined (mass average molecular weight: 800,000, glass transition temperature: -1 ° C), corresponding to the above component (A1).
-Epoxy compound (1): compounding amount = 10.4 parts by mass Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828", epoxy equivalent = 184 to 194 g / eq), corresponding to the above component (B11) ..
-Epoxy compound (2): compounding amount = 5.2 parts by mass Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, product name "Epicron HP-7200HH", epoxy equivalent = 255-260 g / eq), the above component (B11) ) Equivalent.
-Epoxy compound (3): compounding amount = 1.7 parts by mass Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent = 800 to 900 g / eq), equivalent to the above component (B11) ..
-Thermosetting agent: compounding amount = 0.42 parts by mass dicyandiamide (manufactured by ADEKA, product name "ADEKA Hardener EH-3636AS", amount of active hydrogen = 21 g / eq), corresponding to the above component (B12).
-Curing accelerator: compounding amount = 0.42 parts by mass 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemicals Corporation, product name "Curesol 2PHZ"), corresponding to the above component (B13).
Colorant: Blending amount = 0.20 parts by mass Carbon black (manufactured by Mitsubishi Chemical Corporation, product name "# MA650", average particle size = 28 nm), equivalent to the above component (C).
-Silane coupling agent: compounding amount = 0.09 parts by mass 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM403"), corresponding to the above component (D).
-Inorganic filler: compounding amount = 55.5 parts by mass Silica filler (manufactured by Admatex, product name "SC2050MA", average particle size = 0.5 μm), corresponding to the above component (E).

Details of the adhesive resin, the additive, the heat-expandable particles, the release material, and the adhesive resin used in the formation of each layer in the following examples are as follows.

<Adhesive resin>
Acrylic copolymer (i): It has a structural unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio). Acrylic copolymer with Mw 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 of Mw 600,000 having a structural unit derived from a raw material monomer consisting of 0 (mass ratio).

<Additives>
-Isocyanate cross-linking agent (i): manufactured by Tosoh Corporation, product name "Coronate L", solid content concentration: 75% by mass.
-Photopolymerization initiator (i): manufactured by BASF, product name "Irgacure 184", 1-hydroxy-cyclohexyl-phenyl-ketone.

<Thermal expandable particles>
-Thermal expandable particles (i): manufactured by Kureha Co., Ltd., product name "S2640", expansion start temperature (t) = 208 ° C., average particle diameter (D ₅₀ ) = 24 μm, 90% particle diameter (D ₉₀ ) = 49 μm. ..

<Release material>
-Heavy release film: manufactured by Lintec Corporation, product name "SP-PET382150", polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone-based release agent on one side, thickness: 38 μm.
-Light release film: manufactured by Lintec Corporation, product name "SP-PET381031", PET film provided with a release agent layer formed from a silicone-based release agent on one side, thickness: 38 μm.

Example 1
In the adhesive laminate 2b shown in FIG. 2B, a release material was further laminated on the second adhesive layer (X12) of the adhesive sheet (I) and the adhesive layer (X2) of the adhesive sheet (II). An adhesive laminate having a structure was produced by the following procedure.
[1] Preparation of Adhesive Sheet (I) (1-1) Formation of First Adhesive Layer (X11) The isocyanate is added to 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin. A pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass was prepared by blending 5.0 parts by mass (solid content ratio) of the system cross-linking agent (i), diluting with toluene, and stirring uniformly. ..
Then, the pressure-sensitive adhesive composition is applied to the surface of the release agent layer of the heavy-release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to have a non-thermal expansion property having a thickness of 5 μm. A first pressure-sensitive adhesive layer (X11), which is a pressure-sensitive adhesive layer, was formed.
Incidentally, at 23 ° C., the storage shear modulus G of the first pressure-sensitive adhesive layer (X11) '(23) was 2.5 × ¹⁰ 5 Pa.
The adhesive strength of the first pressure-sensitive adhesive layer (X11) measured based on the above method was 0.3 N / 25 mm.

(1-2) Formation of Second Adhesive Layer (X12) To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 0.8 mass of the isocyanate-based cross-linking agent (i) Parts (solid content ratio) were blended, diluted with toluene, and stirred uniformly 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 surface of the release agent layer of the light release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to obtain a second pressure-sensitive adhesive having a thickness of 10 μm. A layer (X12) was formed.
The storage shear elastic modulus G'(23) of the second pressure-sensitive adhesive layer (X12) at 23 ° C. was 9.0 × 10 ⁴ Pa.
The adhesive strength of the second pressure-sensitive adhesive layer (X12) measured based on the above method was 1.0 N / 25 mm.

(1-3) Preparation of Base Material (Y1) To 100 parts by mass of the solid content of the acrylic urethane resin obtained in Production Example 2, 6.3 parts by mass (solid content ratio) of the isocyanate-based cross-linking agent (i) and a catalyst Dioctyl tinbis (2-ethylhexanoate) 1.4 parts by mass (solid content ratio) and the above-mentioned heat-expandable particles (i) were blended as, diluted with toluene, uniformly stirred, and solid content. A resin composition having a concentration (active ingredient concentration) of 30% by mass was prepared.
The content of the heat-expandable particles (i) was 20% by mass with respect to the total amount (100% by mass) of the active ingredient in the obtained resin composition.
Then, the resin is placed on the surface of a polyethylene terephthalate (PET) film having a thickness of 50 μm (manufactured by Toyo Boseki Co., Ltd., product name “Cosmo Shine A4100”, probe tack value: 0 mN / 5 mmφ), which is a non-thermally expandable base material. The composition was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to form a heat-expandable base material layer (Y1-1) having a thickness of 50 μm.
Here, the PET film which is the above-mentioned non-thermally expandable base material corresponds to the non-heat-expandable base material layer (Y1-2).

As a sample for measuring the physical characteristics of the heat-expandable base material layer (Y1-1), the resin composition is applied to the surface of the release agent layer of the light release film to form a coating film, and the coating is applied. The film was dried at 100 ° C. for 120 seconds to form a heat-expandable substrate layer (Y1-1) having a thickness of 50 μm in the same manner.
Then, based on the above-mentioned measuring method, the storage elastic modulus and the probe tack value at each temperature of the heat-expandable base material layer (Y1-1) were measured. The measurement results were as follows.
-Storage modulus at 23 ° C. E'(23) = 2.0 × 10 ⁸ Pa
Storage elastic modulus at 100 ° C. E'(100) = 3.0 × 10 ⁶ Pa
-Storage modulus at 208 ° C. E'(208) = 5.0 × 10 ⁵ Pa
・ Probe tack value = 0mN / 5mmφ

(1-4) Lamination of Each Layer The non-thermally expandable base material layer (Y1-2) of the base material (Y1) prepared in the above (1-3) and the second pressure-sensitive adhesive formed in the above (1-2). The layer (X12) was bonded, and the heat-expandable base material layer (Y1-1) and the second pressure-sensitive adhesive layer (X12) formed in the above (1-2) were bonded.
Then, the light release film / second pressure-sensitive adhesive layer (X12) / non-thermally expandable base material layer (Y1-2) / heat-expandable base material layer (Y1-1) / first pressure-sensitive adhesive layer (X11) / heavy An adhesive sheet (I) was prepared by laminating the release films in this order.

[2] Preparation of Resin Film Forming Sheet (II) The heavy-release film was used as the base material (Y2). A solution of the curable composition prepared in Production Example 3 was applied onto the peel-treated surface of the heavy-release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes to cure to a thickness of 25 μm. A sex resin layer (Z2) was formed.
The adhesive strength of the formed curable resin layer (Z2) was 0.5 N / 25 mm.
Then, the light release film is laminated on the surface of the formed curable resin layer (Z2), and the base material (Y2) / curable resin layer (Z2) / light release film is laminated in this order. A forming sheet (II) was prepared.

[3] Preparation of Adhesive Laminated Body The first pressure-sensitive adhesive layer (X11) exposed by removing the heavy-release film of the pressure-sensitive adhesive sheet (I) produced in [1] above, and the resin film-forming sheet (II). The surface of the heavy-release film, which is the base material (Y2) of the above material (Y2), has not been peeled off, and the adhesive laminate is obtained.

The interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) of the adhesive laminate before and after the heat treatment. The peeling force (F ₁ ) and (F ₂ ) at the time of separation were measured based on the following method.
As a result, the peeling force (F ₀ ) = 200 mN / 25 mm and the peeling force (F ₁ ) = 0 mN / 25 mm, and the ratio of the peeling force (F ₁ ) to the peeling force (F ₀ ) [(F ₁ ) / (F) ₀ )] was 0.

<Measurement of peeling force (F ₀ )>
The prepared adhesive laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and then the heavy release film contained in the adhesive sheet (II) of the adhesive laminate was removed and exposed. The pressure-sensitive adhesive layer (X2) was attached to a stainless steel plate (SUS304, 360 polishing).
Next, the end of the stainless steel plate to which the adhesive laminate was attached was fixed to the lower chuck of a universal tensile tester (manufactured by Orientec, product name "Tencilon UTM-4-100").
Further, the upper chuck of the universal tensile tester is peeled off at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the base material (Y2) of the pressure-sensitive adhesive sheet (II). The adhesive sheet (I) of the adhesive laminate was fixed with.
Then, under the same environment as above, the peeling force measured when peeling at the interface P at a tensile speed of 300 mm / min by the 180 ° peeling method based on JIS Z0237: 2000 is referred to as "peeling force (F ₀ )". ".

<Measurement of peeling force (F ₁ )>
The heavy-release film contained in the adhesive sheet (II) of the produced adhesive laminate was removed, and the exposed adhesive layer (X2) was attached to a stainless steel plate (SUS304, 360 polishing).
Then, the stainless steel plate and the adhesive laminate were heated at 240 ° C. for 3 minutes to expand the thermally expandable particles in the thermally expandable base material layer (Y1-2) of the adhesive laminate.
After that, in the same manner as the measurement of the peeling force (F ₀ ) described above, under the above conditions, the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are combined. The peeling force measured when peeling at the interface P was defined as "peeling force (F ₁ )".
In the measurement of the peeling force (F ₁ ), when the adhesive sheet (I) of the adhesive laminate was to be fixed by the upper chuck of the universal tensile tester, the adhesive sheet (I) was completely separated at the interface P. If the fixing was not possible, the measurement was terminated and the peeling force (F ₁ ) at that time was set to "0 mN / 25 mm".

Example 2
A cured sealant with a cured resin film was prepared by the following procedure.
(1) Placement of semiconductor chip The light release film on the adhesive sheet (I) side of the adhesive laminate produced in Example 1 was removed, and the exposed adhesive sheet (I) was exposed to the second adhesive layer (X12). ) Was attached to the support (glass).
Then, the light release film on the resin film forming sheet (II) side was also removed, and nine semiconductor chips (each) were placed on the surface of the curable resin layer (Z2) of the exposed resin film forming sheet (II). The chip size is 6.4 mm x 6.4 mm, and the chip thickness is 200 μm (# 2000)) at the required intervals so that the back surface of each semiconductor chip opposite to the circuit surface is in contact with the surface. It was placed.

(2) Formation of Curing Encapsulant The nine semiconductor chips and the surface of the curable resin layer (Z2) at least in the peripheral portion of the semiconductor chip are coated with a sealing resin film, and a vacuum heating and pressurizing laminator. (“7024HP5” manufactured by ROHM and HAAS) was used to cure the sealing resin film to prepare a cured sealing body.
The sealing conditions are as follows.
・ Preheating temperature: 100 ° C for both table and diaphragm
・ Vacuuming: 60 seconds ・ Dynamic press mode: 30 seconds ・ Static press mode: 10 seconds ・ Sealing temperature: 180 ° C x 60 minutes As the sealing resin film cures, the resin film forming sheet (II) The curable resin layer (Z2) was also cured in the above environment to obtain a cured resin film.

(3) Separation at Interface P After the above (2), the adhesive laminate was heat-treated at 240 ° C., which is equal to or higher than the expansion start temperature (208 ° C.) of the heat-expandable particles, for 3 minutes. Then, the pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) could be easily separated at the interface P.
Then, after separation, the base material (Y2) of the resin film forming sheet (II) was also removed to obtain a cured encapsulant with a cured resin film.

1a, 1b, 1c, 1d, 2 Adhesive laminate (I) Adhesive sheet (X1) Adhesive layer (X11) First adhesive layer (X12) Second adhesive layer (Y1) Base material (Y1-1) Thermo-expandable base material layer (Y1-2) Non-heat-expandable base material layer (II) Resin film forming sheet (Y2) Base material (Z2) Curable resin layer 50 Support 60 Processed object P Interface

Claims (13)

A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1) and containing heat-expandable particles in any of the layers,
A resin film forming sheet (II) having a base material (Y2) and a curable resin layer (Z2) is provided.
The adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) are directly laminated.
An adhesive laminate used to fix an object to be processed to a support when performing a predetermined process.
The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support.
The surface of the curable resin layer (Z2) of the resin film forming sheet (II) is a surface to which the object to be processed is attached.
By heat treatment at a temperature equal to or higher than the thermal expansion start temperature (t) of the thermally expandable particles, the adhesive sheet (I) can be separated at the interface P between the base material (Y2) of the resin film forming sheet (II). Is an adhesive laminate. The adhesive laminate according to claim 1, wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270 ° C. The adhesive laminate according to claim 1 or 2, wherein the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) containing the heat-expandable particles. The adhesiveness according to claim 3, wherein the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2). Laminated body. A claim in which the heat-expandable base material layer (Y1-1) of the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated. The adhesive laminate according to 3 or 4. The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12).
It has a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
The adhesive laminate according to any one of claims 3 to 5, wherein the surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface to be attached to the support. The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12).
The first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles.
The second pressure-sensitive adhesive layer (X12) is a non-thermally expandable pressure-sensitive adhesive layer.
It has a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated.
The adhesive laminate according to claim 1 or 2, wherein the surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface to be attached to the support. The adhesive laminate according to any one of claims 1 to 7, wherein the surface on the side where the adhesive sheet (I) of the base material (Y2) is laminated is a surface that has been subjected to a peeling treatment. The curable resin layer (Z2) is a layer formed from a curable composition (z) containing a polymer component (A) and a curable component (B), according to any one of claims 1 to 8. The adhesive laminate according to the description. A method for producing a processed object with a resin film by using the adhesive laminate according to any one of claims 1 to 9.
A method for producing a processed object with a resin film, which comprises the following steps (α-1) to (α-3).
Step (α-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. Step / step (α-2) of placing or affixing the object to be processed on the surface of Z2): Step / step (α-3) of performing a predetermined process on the object to be processed: heat of the heat-expandable particles A step of separating the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) at the interface P by heating at the expansion start temperature (t) or higher to obtain a processed object with a resin film. The method for producing a processed object with a resin film according to claim 10, wherein in the step (α-2), the curable resin layer (Z2) is cured to form a cured resin film. The method for producing a processed object with a resin film according to claim 10, further comprising the following step (α-2') after the step (α-2) and before the step (α-3).
-Step (α-2'): A step of curing the curable resin layer (Z2) to form a cured resin film. A method for producing a cured encapsulant with a cured resin film using the adhesive laminate according to any one of claims 1 to 9.
A method for producing a cured encapsulant with a cured resin film, which comprises the following steps (β-1) to (β-3).
Step (β-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to the support, and the curable resin layer (II) of the resin film-forming sheet (II) is attached. Step / Step (β-2) of placing a semiconductor chip on Z2): The semiconductor chip is coated with a sealing material, the sealing material is cured, and the semiconductor chip is sealed. Step / Step (β-3) of curing the body and the curable resin layer (Z2) to form a curable resin film: Adhesion by heating the thermosetting particles at a thermal expansion start temperature (t) or higher. A step of separating the sheet (I) and the base material (Y2) of the resin film forming sheet (II) at the interface P to obtain a cured encapsulant with a cured resin film.