TW201934698A - Adhesive layered body, method for manufacturing object to be processed with resin film, and method for manufacturing hardened sealing body with hardened resin film - Google Patents

Abstract

Provided is an adhesive layered body comprising: a thermally expandable adhesive sheet (I) that includes a substrate (Y1) and an adhesive layer (X1), either of which contains thermally expandable particles; and a resin film forming sheet (II) that includes a substrate (Y2) and a hardening resin layer (Z2). The adhesive layered body is formed by directly layering the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II), and the adhesive layered body is used to secure an object to be processed to a support body when prescribed processing is performed thereon. The adhesive layered body is separable at an interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) by heating treatment at the temperature of at least the thermal expansion start temperature (t) of the thermally expandable particles.

Description

Manufacturing method of adhesive laminated body, processing object with resin film, and manufacturing method of hardened package body with cured resin film

The present invention relates to a method for producing an adhesive laminated body and a processing object with a resin film using the adhesive laminated body, and a method for producing a cured package with a cured resin film.

The adhesive sheet is not only used for semi-permanent fixing of members, but also used for temporary fixing of temporary fixing of a target member when processing or inspecting building materials, interior materials, and electronic parts.
This kind of adhesive sheet for temporary fixed use is required to have both adhesiveness during use and peelability after use.

For example, Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporary fixation of an electronic component provided with a thermally expandable adhesive layer containing a thermally expandable microsphere on at least one side of a base material at the time of cutting.
For this heat-peelable adhesive sheet, the maximum particle diameter of the thermally expandable microspheres is adjusted for the thickness of the thermally expandable adhesive layer, and the average roughness of the centerline of the surface of the thermally expandable adhesive layer before heating is adjusted to 0.4 μm or less.
Patent Document 1 describes that this heat-peelable adhesive sheet can ensure the contact area with the adherend when the electronic component is cut, so it can exhibit unsatisfactory adhesiveness that can prevent the wafer from flying out, etc. The heat-expandable microspheres are expanded by heating, reducing the contact area with the adherend, and can be easily peeled off.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent No. 3985853

[Problems to be Solved by the Invention]

In the processing step using the adhesive sheet as described in Patent Document 1, the adhesive sheet is used to temporarily fix the object to be processed (hereinafter also referred to as "processing object"), and the object to be processed is processed. Separation of self-adhesive flakes.
However, in particular, in the manufacture of electronic parts, multiple processing steps are often performed.
When a plurality of processing steps are required for the processing object, after the processing object is separated from the adhesive sheet after processing, it may be adhered to the new adhesive sheet again for processing in the next step.

However, the operation of attaching the processing object to the new adhesive sheet every step is troublesome, and at the same time, the productivity of the product is reduced.
For example, when a processing object such as a semiconductor wafer subjected to predetermined processing is adhered to an adhesive sheet, a cured resin film may be formed in order to protect the back side of the processing object or to provide die with a bonding function. For this purpose, a sheet for forming a resin film having a curable resin layer may be used.
At this time, generally, after the object to be processed is separated from the adhesive sheet, a separately prepared film for forming a resin film having a curable resin layer is adhered to the object to be processed to harden the curable resin layer to form a cured resin film. .
In other words, in order to obtain an object to be processed with a resin film, it is necessary to apply two adhesion operations to a predetermined adhesive sheet for processing and a resin film forming sheet for forming a cured resin film.

The object of the present invention is to provide a processing object that can be fixed to a support body and carry out predetermined processing. At the same time, after processing, it can be easily separated from the support body at one time with only a slight force, and by separating from the support body, a resin film can be obtained Adhesive laminated body of the processing object.

[Means to solve the problem]

The present inventors have found that they include a substrate and an adhesive layer, and one of the layers includes a thermally expandable adhesive sheet (I) containing thermally expandable particles, and a resin film forming sheet (II) having a substrate and a curable resin layer. In addition, the adhesive laminated body obtained by directly laminating the base material of the adhesive sheet (I) and the resin film forming sheet (II) can solve the above problems.

That is, the present invention relates to the following [1] to [13].
[1] An adhesive laminated body comprising: a substrate (Y1) and an adhesive layer (X1), one of which includes a thermally expandable adhesive sheet (I) having thermally expandable particles,
A sheet (II) for forming a resin film having a base material (Y2) and a curable resin layer (Z2),
The adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated,
Adhesive laminated body for fixing a processing object to a support body when performing specific processing,
The surface of the adhesive layer (X1) of the adhesive sheet (I) is a surface which is adhered 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 adhered,
By the heat treatment at a temperature higher than the thermal expansion start temperature (t) of the thermally expandable particles, the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) can be separated.
[2] The adhesive laminated body 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 laminate according to the above [1] or [2], wherein the base material (Y1) of the adhesive sheet (I) is a heat-expandable base material layer (Y1-1) including the heat-expandable particles. .
[4] The adhesive laminate according to the above [3], wherein the substrate (Y1) included in the adhesive sheet (I) is a substrate having a thermally expandable substrate (Y1-1) and a layer having a non-thermally expandable substrate (Y1- 2).
[5] The adhesive laminate according to the above [3] or [4], wherein the heat-expandable substrate layer (Y1-1) of the substrate (Y1) included in the adhesive sheet (I) and the sheet for forming a resin film ( II) The substrate (Y2) is directly laminated.
[6] The adhesive laminate according to any one of the above [3] to [5], wherein the adhesive sheet (I) is held by the first adhesive layer (X11) and the second adhesive layer (X12). The structure of the substrate (Y1),
The first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated,
The surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface adhered to the support.
[7] The adhesive laminated body according to the above [1] or [2], wherein the adhesive sheet (I) has a first adhesive layer (X11) and a second adhesive layer (X12), and holds the substrate (Y1) ),
The first adhesive layer (X11) is a thermally expandable adhesive layer containing the aforementioned thermally expandable particles,
The second adhesive layer (X12) is a non-thermally expandable adhesive layer,
The first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated,
The surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface adhered to the support.
[8] The adhesive laminate according to any one of the above [1] to [7], wherein the surface of the substrate (Y2) on the side having the adhesive sheet (I) is a surface to which a peeling treatment is applied.
[9] The adhesive laminate according to any one of the above [1] to [8], wherein the curable resin layer (Z2) is a curable composition containing a polymer component (A) and a curable component (B) (Z).
[10] A method for manufacturing a processing object with a resin film, which is a method for manufacturing a processing object with a resin film by using the adhesive laminated body according to any one of [1] to [9] above,
It has the following steps (α-1) ~ (α-3):
Step (α-1): The surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate is adhered to the support, and at the same time, the curable resin layer (II) of the resin film forming sheet (II) ( Z2) The step of placing or adhering the processing object on the surface,
Step (α-2): a step of performing a specific processing on the aforementioned processing object,
Step (α-3): A separation occurs at the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) by heating above the thermal expansion start temperature (t) of the thermally expandable particles. , A step of obtaining a processing object with a resin film.
[11] The method for producing a processing object with a resin film according to the above [10], wherein in the step (α-2), the curable resin layer (Z2) is cured to form a cured resin film.
[12] The method for manufacturing an object to be processed with a resin film as described in [10] above, which includes the following step (α-2 ') after step (α-2) and before 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 manufacturing a hardened package with a hardened resin film, which is a method for manufacturing a hardened package with a hardened resin film by using the adhesive laminated body according to any one of [1] to [9] above,
It has the following steps (β-1) ~ (β-3):
Step (β-1): The surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate is adhered to the support, and at the same time, the semiconductor wafer is placed on the resin film-forming sheet (II). Step of hardening resin layer (Z2),
Step (β-2): a step of covering the semiconductor wafer with a sealing material, curing the sealing material, forming a hardened package in which the semiconductor wafer is encapsulated, and curing the hardening resin layer (Z2) to form a hardened resin film,
Step (β-3): separation occurs at the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) by heating above the thermal expansion start temperature (t) of the thermally expandable particles. , A step of obtaining a hardened package with a hardened resin film.

[Inventive effect]

The adhesive laminated body of the present invention can fix the processing object to the support and perform the predetermined processing. At the same time, it can be easily separated from the support at one time with only a slight force after processing, and can be obtained by separating from the support. Object of resin film processing.

[Form of Implementing Invention]

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

In the present specification, "active ingredient" means a component included in a target composition and excluding a diluted solvent.
In this specification, the mass average molecular weight (Mw) is a value converted into a standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically, a value measured according to a method described in Examples.
In this specification, for example, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and the same applies to other similar terms.
In the present specification, the lower limit value and the upper limit value of the stepwise description regarding the preferred numerical range (for example, the range of the content, etc.) may be independently combined. For example, from the description of "preferably 10 ~ 90, more preferably 30 ~ 60", combining "better lower limit (10)" and "better upper limit (60)" can form "10 ~ 60 ".

[Composition of Adhesive Laminate]
The adhesive laminate system of the present invention includes a thermally expandable adhesive sheet (I) having a substrate (Y1) and an adhesive layer (X1), one of which includes thermally expandable particles,
A sheet (II) for forming a resin film having a base material (Y2) and a curable resin layer (Z2), wherein the adhesive sheet (I) and the base material (Y2) of the sheet (II) for forming a resin film are directly laminated, When a specific processing is performed, it can be used to fix a processing object to a support.

In the adhesive laminated body of the present invention, the surface of the adhesive layer (X1) of the adhesive sheet (I) is a surface that is adhered to the support.
In other words, the adhesive sheet (I) has at least one adhesive layer (X1), and the surface of one of the adhesive layers (X1) is adhered to the surface of the support.
When the adhesive sheet (I) has a first adhesive layer (X11) and a second adhesive layer (X12) on both sides of the substrate (Y1), the surface of the second adhesive layer (X12) is adhered to the support. The surface of the first adhesive layer (X11) is a surface to be adhered to the substrate (Y2) of the resin film forming sheet (II).

The surface of the curable resin layer (Z2) of the resin film-forming sheet (II) is a surface to which an object to be processed is adhered. The hardening resin layer (Z2) is a hardenable resin layer, and a hardening resin film can be formed by applying a hardening treatment. The hardening treatment may be performed at the same time as the predetermined processing is performed, or may be performed after the predetermined processing is performed.

In addition, the adhesive laminate of the present invention is subjected to a heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the thermally expandable particles, to the substrate (Y2) of the adhesive sheet (I) and the resin film-forming sheet (II). The interface P can be separated. In the following description, this heat treatment is also referred to as "separation heat treatment".
Therefore, by using the adhesive laminated body of the present invention, the object to be processed is fixed to the support, the object to be processed is subjected to predetermined processing, and then the above-mentioned heat treatment is performed to separate at the interface P to obtain a sheet for forming a resin film. (II) A processing object with a resin film laminated on the processing object.
Here, the object to be processed with the resin film may be the object to be processed with the hardened resin layer formed by curing the hardening resin layer (Z2), or the hardenable resin layer (Z2) may be the non-hardened hardening resin. Film processing object.
In the following description, the "resin film" refers to both the "curable resin film" formed by curing the curable resin layer (Z2) and the "curable resin film" where the curable resin layer (Z2) is uncured.

1 to 3 are schematic cross-sectional views showing the constitutions of the adhesive laminated body according to the first aspect, the second aspect, and the third aspect of the present invention. Hereinafter, the structure of the adhesive laminated body according to one aspect of the present invention will be described with reference to FIGS. 1 to 3 as appropriate.

＜ Adhesive laminated body of the first aspect ＞
Examples of the adhesive laminates according to the first aspect of the present invention include the adhesive laminates 1a and 1b shown in FIGS. 1 (a) and (b).
The adhesive laminates 1a and 1b are for forming a resin film including an adhesive sheet (I) having a substrate (Y1) and an adhesive layer (X1), and a substrate (Y2) and a curable resin layer (Z2). The sheet (II) has a structure in which a substrate (Y1) to which the sheet (I) is adhered and a substrate (Y2) of the resin film-forming sheet (II) are directly laminated.

The adhesive multilayer system of the present invention uses any one of the adhesive sheet (I) as a layer containing thermally expandable particles, so that it can be separated at the interface P by heat treatment for separation.
By the heat treatment for separation of the adhesive multilayer system of the present invention, the thermally expandable particles are expanded, and the surface of the layer containing the thermally expandable particles is uneven. Therefore, the contact area between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) is reduced.
As a result, the object to be processed was adhered to the surface of the curable resin layer (Z2) of the resin film forming sheet (II), and after a specific process was performed, the base of the adhesive sheet (I) and the resin film forming sheet (II) The interface P of the material (Y2) is separated to obtain a processing object adhered to the resin film forming sheet (II).

Therefore, the adhesive laminated body of the present invention can fix the processing object to the support body through the adhesive laminated body, perform the predetermined processing, and at the same time after performing the predetermined processing, it can be easily separated from the support at one time. This processing object. After separation from the support, an object to be processed with a sheet for forming a resin film can be obtained.
Therefore, the use of the adhesive laminated body of the present invention has the following advantages, for example.
In the next step, there is no need to attach a sheet for forming a resin film to the processed object after separation.
Even if the object to be processed is thin and fragile, since the sheet for forming a resin film is adhered to the object to be processed, support performance is provided, and the operability for the next step of transportation is good.

In the first aspect of the present invention, the base material (Y1) is an adhesive laminated body 1a, 1b as shown in FIG. 1, and it is preferable to have a heat-expandable base material layer (Y1-1) containing heat-expandable particles.
Moreover, the base material (Y1) is an adhesive laminated body 1a as shown in FIG. 1 (a), and may be a single-layer structure which has only the heat-expandable base material layer (Y1-1) containing a heat-expandable particle.
The substrate (Y1) is an adhesive laminate 1b as shown in FIG. 1 (b), and may be a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). Of multiple layers.

The adhesive laminated body 1a shown in FIG. 1 (a) is subjected to heat treatment for separation, and the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) expand, and the substrate ( The surface on the resin film-forming sheet (II) side of Y1) is uneven, and the contact area between the substrate (Y1) and the substrate (Y2) of the resin film-forming sheet (II) is reduced.
In addition, since the adhesive layer (X1) included in the adhesive laminated body 1a is adhered to the support, it is difficult to form irregularities on the surface of the substrate (Y1) on the adhesive layer (X1) side. Therefore, the surface of the base material (Y1) which is in contact with the resin film-forming sheet (II) can be efficiently formed with irregularities.
As a result, the adhesive laminate 1a can be easily separated at a time with a slight force at the interface P between the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II).
Moreover, it can also be designed by forming the adhesive layer (X1) which the adhesive laminated body 1a has from the adhesive composition which becomes high adhesive force to a support body, and it can isolate | separate more easily at the interface P.

In addition, the adhesive laminated body 1b shown in FIG. 1 (b) is subjected to heat treatment for separation, and the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) swell, and the substrate The surface of the resin film forming sheet (II) side of the material (Y1) is uneven, and the contact area between the substrate (Y1) and the substrate (Y2) of the resin film forming sheet (II) is reduced.
The non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion by heat treatment, so it is difficult to form the surface on the adhesive layer (X1) side of the base material (Y1). Bump. Therefore, the surface on the resin film-forming sheet (II) side of the substrate (Y1) can be efficiently formed with unevenness.
As a result, the adhesive laminate 1b can be easily separated at a time with a slight force at the interface P between the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II).

From the above point of view, in the first aspect of the present invention, as shown in (b) of the adhesive laminated body 1b, one surface side of the substrate (Y1) has a thermally expandable substrate layer (Y1-1), and the other It is preferable to have a non-thermally expandable base material layer (Y1-2) on the surface side.

In addition, in the first aspect of the present invention, from the viewpoint that the adhesive laminate can be easily separated at a time with a slight force at the interface P, the adhesive laminates 1a and 1b are those possessed by the adhesive sheet (I). The thermally expandable substrate layer (Y1-1) of the substrate (Y1) and the substrate (Y2) of the resin film-forming sheet (II) are preferably laminated directly.

＜ Adhesive Laminated Body of Second Aspect ＞
Examples of the adhesive laminated body according to the second aspect of the present invention include the adhesive laminated bodies 1c and 1d shown in FIGS. 2 (a) and (b).
The adhesive laminates 1c and 1d shown in FIG. 2 are adhesive sheets (I) having a structure in which a substrate (Y1) is held by a first adhesive layer (X11) and a second adhesive layer (X12). The first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated.
Moreover, in the adhesive laminated body 1c, 1d, the surface of the 2nd adhesive layer (X12) is the surface which adhered to the said support body.

In a second aspect of the present invention, it is preferable that the base material (Y1) is a heat-expandable base material layer (Y1-1) having heat-expandable particles, as shown in the adhesive laminates 1c and 1d shown in FIG. 2.
Moreover, the base material (Y1) is an adhesive laminated body 1c as shown in FIG. 2 (a), and may be a single-layer structure which has only the heat-expandable base material layer (Y1-1) containing a heat-expandable particle. The substrate (Y1) is an adhesive laminate 1d as shown in FIG. 2 (b), and may be a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). Stratified composition.
When the base material (Y1) has a multi-layered structure including a thermally expandable base material layer (Y1-1) and a non-thermally expandable base material layer (Y1-2), the thermally expandable base material layer (Y1-1) is arranged. On the resin film forming sheet (II) side, it is preferable that the non-thermally expandable substrate layer (Y1-2) is disposed on the second adhesive layer (X12) side.

The adhesive laminated body 1c shown in Fig. 2 (a) is a heat-expansible particle constituting the base material (Y1) in the heat-expandable base material layer (Y1-1), which expands due to the heat treatment for separation, and the first adhesive The surface of the substrate (Y1) on the layer (X11) side is uneven. In addition, due to the unevenness on the surface of the substrate (Y1), the first adhesive layer (X11) is also pushed up, and the surface of the first adhesive layer (X11) on the resin film forming sheet (II) side is also formed. Bump. Therefore, the contact area between the first adhesive layer (X11) and the substrate (Y2) of the resin film-forming sheet (II) is reduced.
The second adhesive layer (X12) included in the adhesive laminated body 1c is adhered to the support, so it is difficult for the surface on the second adhesive layer (X12) side of the substrate (Y1) to be uneven. Therefore, unevenness is efficiently formed on the surface of the first adhesive layer (X11) side of the base material (Y1), and unevenness is easily formed on the surface of the first adhesive layer (X11).
As a result, at the interface P of the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II), the adhesive laminated body 1c can be easily separated at a time with a slight force.
Alternatively, the second adhesive layer (X12) included in the adhesive laminated body 1c may be formed by an adhesive composition having a higher adhesive force with respect to the support, and it may be easier at the interface P. Separation.

In addition, the adhesive laminated body 1d shown in FIG. 2 (b) is subjected to heat treatment for separation to expand the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1), and the substrate The surface of the first adhesive layer (X11) of the material (Y1) is uneven. In addition, due to the unevenness on the surface of the substrate (Y1), the first adhesive layer (X11) is also pushed upward, and the surface on the resin film forming sheet (II) side of the first adhesive layer (X11) is also pushed up. Formation of bumps. Therefore, the contact area between the first adhesive layer (X11) and the substrate (Y2) of the resin film-forming sheet (II) is reduced.
The non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion by heat treatment, so the surface on the second adhesive layer (X12) side of the base material (Y1) is difficult to form. Bump. Therefore, the surface on the first adhesive layer (X11) side of the base material (Y1) can be efficiently formed with unevenness.
As a result, the adhesive laminate 1d can be easily separated at a time with a slight force at the interface P between the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II).

Here, the second aspect of the present invention is an adhesive laminated body which can be easily separated at a time with a slight force at the interface P, and the adhesive laminated bodies 1c and 1d are the basis of the adhesive sheet (I). It is preferable that the thermally expandable base material layer (Y1-1) of the material (Y1) and the first adhesive layer (X11) are laminated directly. In this case, further, a constitution in which the first adhesive layer (X11) and the base material (Y2) of the resin film forming sheet (II) are directly laminated is more preferable.

＜ Third aspect of adhesive laminar body ＞
The adhesive laminates 1a, 1b of the first aspect of the present invention, and the adhesive laminates 1c, 1d of the second aspect of the present invention are all one of the layers constituting the substrate (Y1), which contain thermal expansion properties. Particle layer.
In the third aspect of the present invention, the adhesive laminate can be provided with a thermally expandable adhesive layer containing the aforementioned thermally expandable particles on the surface of the interface P side of the substrate (Y1) of the adhesive sheet (I), and the substrate ( Y1) has a structure in which a non-thermally expandable adhesive layer is provided on the other surface.
Examples of this aspect include, for example, the adhesive laminate 2 shown in FIG. 3, and the adhesive sheet (I) has a first adhesive layer (X11) and a second adhesive layer (X12), and holds the substrate. (Y1), the first adhesive layer (X11) is a thermally expandable adhesive layer containing thermally expandable particles, the second adhesive layer (X12) is a non-thermally expandable adhesive layer, and has the first 1 A component in which an adhesive layer (X11) and a substrate (Y2) of a resin film forming sheet (II) are directly laminated.
Furthermore, in the above-mentioned configuration of the adhesive laminated body 2, the surface of the second adhesive layer (X12) is a surface to be adhered to the support.
Moreover, in the above-mentioned structure of the adhesive laminated body 2, it is preferable that the base material (Y1) is a non-thermally expandable base material.

The adhesive laminated body 2 shown in FIG. 3 is subjected to a heat treatment for separation to cause unevenness on the surface of the thermally expandable adhesive layer of the first adhesive layer (X11), and the first adhesive layer (X11) and the resin film are formed. The contact area of the substrate (Y2) using the sheet (II) is reduced.
On the other hand, the surface of the first adhesive layer (X11) on the substrate (Y1) side is a substrate (Y1) on which a non-thermally expandable substrate is laminated, so that unevenness is unlikely to occur. Therefore, the surface of the first adhesive layer (X11) on the resin film-forming sheet (II) side is formed with unevenness efficiently.
As a result, at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II), the adhesive laminate 2 can be easily separated at a time with a slight force.

<Configuration of Adhesive Laminated Body with Release Material>
In one aspect of the present invention, one or both of the surface of the adhesive layer (X1) of the support and the surface of the hardening resin layer (Z2) of the object to be processed may be adhered. , And then laminated the composition of the release material.
For example, the adhesive surface of one of the adhesive layer (X1) and the hardening resin layer (Z2) in the adhesive laminates 1a and 1b shown in FIGS. 1 (a) and (b) may be provided in the two area layers. The peeling material after the peeling treatment is applied is rolled into a roll. The adhesive laminates 1c and 1d shown in Figs. 2 (a) and 2 (b), and the adhesive laminate 2 shown in Fig. 3 may be similarly rolled.

[Various physical properties of adhesive laminates]
According to one aspect of the present invention, the adhesive laminate system is subjected to heat treatment at a temperature higher than the expansion start temperature (t) of the thermally expandable particles, and is applied to the substrate (I) and the resin film-forming sheet (II) substrate ( The interface P of Y2) can be easily separated at one time with slight force.
Here, in the adhesive laminated body of one aspect of the present invention, the peeling force (F ₁ ) when the interface P is separated by a heat treatment at a temperature higher than the expansion start temperature (t) of the thermally expandable particles is usually 0 ~ 2000mN / 25mm, preferably 0 ~ 1000mN / 25mm, more preferably 0 ~ 150mN / 25mm, still more preferably 0 ~ 100mN / 25mm, and even more preferably 0 ~ 50mN / 25mm.
In addition, even 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 is too small to measure.

In addition, from the viewpoint of sufficiently fixing the object to be processed before the heat treatment to avoid adverse effects on the processing work, the interlayer adhesion between the adhesive sheet (I) and the resin film-forming sheet (II) is high. Those are better.
In view of the above point, in the adhesive multilayer body of one aspect of the present invention, the peeling force (F ₀ ) at the interface P separation before heat treatment is preferably 100 mN / 25 mm or more, and more preferably 130 mN / 25 mm or more. It is more preferably 160mN / 25mm or more, and more preferably 50,000mN / 25mm or less.

In the adhesive laminated body according to one aspect of the present invention, the peeling force (F ₀ ) is greater 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, and even more preferably 0 to 0.5, and 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 a temperature at which the thermally expandable particles swell.
The temperature condition at the time of measuring the peeling force (F ₀ ) may be any temperature as long as it does not reach the expansion start temperature (t), and is basically room temperature (23 ° C).
However, more specific measurement conditions and measurement methods of the peeling force (F ₁ ) and the peeling force (F ₀ ) are based on the methods described in the examples.

In the adhesive laminate of one aspect of the present invention, the adhesive layer (X1) (the first adhesive layer (X11) and the second adhesive layer) possessed by the adhesive sheet (I) at room temperature (23 ° C) (X12)), preferably 0.1 ~ 10.0 N / 25mm, more preferably 0.2 ~ 8.0N / 25mm, more preferably 0.4 ~ 6.0N / 25 mm, and even more preferably 0.5 ~ 4.0N / 25mm .
When the adhesive sheet (I) has the first adhesive layer (X11) and the second adhesive layer (X12), the adhesive forces of the first adhesive layer (X11) and the second adhesive layer (X12) are smaller in the above ranges, respectively. The second adhesive layer (X12) adhered to the support is higher than the first adhesive layer (X11) from the viewpoint that the adhesiveness with the support is improved, and the interface P can be more easily separated at one time. Better adhesion.

Moreover, in the adhesive laminated body according to one aspect of the present invention, from the viewpoint of improving the adhesion with the adhered processing object, the resin film forming sheet (II) has a hardening resin layer (Z2). It is preferable that the surface has adhesion.
Specifically, the adhesive force of the curable resin layer (Z2) possessed by the resin film-forming sheet (II) at room temperature (23 ° C) is preferably 0.01 to 5 N / 25 mm, and more preferably 0.05 to 4 N / 25mm, and more preferably 0.1 ~ 3N / 25mm.

In this specification, the adhesive force of the adhesive layer (X1) (the first adhesive layer (X11) and the second adhesive layer (X12)) and the curable resin layer (Z2) refers to those described in the examples. The value measured by the method.

The substrate (Y1) included in the adhesive sheet (I) and the substrate (Y2) included in the resin film-forming sheet (II) are non-adhesive substrates.
In the present invention, the determination of the non-adhesive substrate is based on the surface of the target substrate. When the probe-type initial tack force measured according to JIS Z0237: 1991 is less than 50mN / 5mmf, the substrate is judged as "Non-adhesive substrate".
The probe-type initial adhesion on the surface of the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) used in one aspect of the present invention is independent of each other. It is usually less than 50mN / 5mmf, preferably less than 30mN / 5mmf, more preferably less than 10mN / 5mmf, and even more preferably less than 5mN / 5mmf.
In this specification, the specific measurement method of the probe-type initial viscosity of the surface of the thermally expandable substrate is based on the method described in the examples.

Hereinafter, each layer which comprises the adhesive laminated body of this invention is demonstrated.

[Composition of Adhesive Sheet (I)]
The adhesive sheet (I) of the adhesive laminated body of the present invention has a substrate (Y1) and an adhesive layer (X1), and can be bonded to the base of the resin film-forming sheet (II) by heat treatment for separation. The interface of the material (Y2) is separable, and one layer contains the thermally expandable adhesive sheet of the thermally expandable particles.
In one aspect of the present invention, the thermal expansion start temperature (t) of the thermally expandable particles is preferably 60 to 270 ° C.

The adhesive sheet (I) used in one aspect of the present invention is preferably the following aspect.
Adhesive sheet (I) of the first aspect: An adhesive sheet (I) having a thermally expandable substrate layer (Y1-1) containing thermally expandable particles as a substrate (Y1).
Adhesive sheet (I) of the second aspect: on both sides of the substrate (Y1), a first adhesive layer (X11) having a thermally expandable adhesive layer containing thermally expandable particles and a non-thermally expandable adhesive layer Adhesive sheet (I) of the second adhesive layer (X12).
The substrate (Y1) is an adhesive sheet (I) of a non-thermally expandable substrate.
The first aspect and the second aspect of the adhesive sheet (I) used in one aspect of the present invention will be described below.

＜ Adhesive sheet of the first aspect (I) ＞
The first aspect of the adhesive sheet (I) is shown in FIGS. 1 and 2, and the substrate (Y1) is a material having a thermally expandable substrate layer (Y1-1) containing thermally expandable particles.

In the first aspect of the adhesive sheet (I), the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) can be easily separated at one time with a slight force. The layer (X1) is preferably a non-thermally expandable adhesive layer.
Specifically, it is preferable that the adhesive layer (X1) in the adhesive sheet (I) included in the adhesive laminates 1a and 1b shown in FIG. 1 is a non-thermally expandable adhesive layer. In addition, the adhesive sheets (I) of the adhesive laminates 1c and 1d shown in FIG. 2 are preferably the first non-thermally expandable adhesive layer (X11) and the second adhesive layer (X12). .

The thickness of the substrate (Y1) of the first aspect of the adhesive sheet (I) before the heat treatment is preferably 10 to 1000 μm, more preferably 20 to 700 μm, and still more preferably 25 to 500 μm. It is preferably 30 to 300 μm.

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

In this specification, for example, as shown in FIG. 2, when the adhesive sheet (I) is a plurality of adhesive layers, the “thickness of the adhesive layer (X1)” means the thickness of each adhesive layer (FIG. 2). (The respective thicknesses of the adhesive layers (X11) and (X12)).
In addition, in this specification, the thickness of each layer which comprises an adhesive laminated body means the value measured by the method as described in an Example.

In the first aspect of the adhesive sheet (I), before the heat treatment for separation, the thickness ratio [(Y1-1) / (X1)] of the thermally expandable substrate layer (Y1-1) to the adhesive layer (X1), It is preferably 1,000 or less, more preferably 200 or less, still more preferably 60 or less, and still more preferably 30 or less.
When the thickness ratio is 1000 or less, it can be formed at the interface P of the substrate (Y2) of the adhesive sheet (I) and the resin film forming sheet (II) by heat treatment, and the adhesiveness can be easily separated at a time with a slight force. Laminated body.
The thickness is more preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 5.0 or more.

In addition, in the first aspect of the adhesive sheet (I), the base material (Y1) is as shown in FIG. 1 (a), and may be composed of only a thermally expandable base material layer (Y1-1), as shown in FIG. 1 ( As shown in b), the resin film-forming sheet (II) may have a heat-expandable base material layer (Y1-1) and an adhesive layer (X1) side may have a non-heat-expandable base material layer (Y1-2). By.

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

＜ Adhesive sheet of the second aspect (I) ＞
As the second aspect of the adhesive sheet (I), as shown in FIG. 3, the first adhesive layer (X11) and the first adhesive layer (X11) each having a thermally expandable adhesive layer containing thermally expandable particles on both sides of the substrate (Y1) and The second adhesive layer (X12) of the non-thermally expandable adhesive layer.
The first adhesive layer (X11) of the second aspect of the adhesive sheet (I) is a thermally expandable adhesive layer, and the substrate (Y2) of the resin film forming sheet (II) is in direct contact.
In the second aspect of the adhesive sheet (I), the substrate (Y1) is preferably a non-thermally expandable substrate layer.

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

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

The thermally expandable particles contained in any of the layers constituting the adhesive sheet (I) will be described below, and the thermally expandable substrate layer (Y1-1) and the non-thermally expandable substrate layer (Y1-2) constituting the substrate (Y1) will be described in detail. , And adhesive layer (X1).

＜ thermally expandable particles ＞
The thermally expandable particles used in the present invention may be particles that are expanded by heating, but are preferably adjusted to particles having an expansion start temperature (t) of 60 to 270 ° C. The expansion start temperature (t) is suitable for the application of the adhesive laminate.
In addition, in this specification, the expansion start temperature (t) of a thermally expandable particle means the value measured by the following method.

(Measurement method of the expansion start temperature (t) of thermally expandable particles)
A 0.5 mm diameter (inner diameter 5.65 mm) and 4.8 mm depth aluminum cup was charged with 0.5 mg of thermally expandable particles as a measurement target, and an aluminum lid (5.6 mm in diameter and 0.1 mm in thickness) was placed on the sample.
For this sample, a dynamic viscoelasticity measuring device was used. The height of the sample was measured in a state where a force of 0.01 N was applied from the upper part of the aluminum cover by a pressurizer. In addition, under the state of applying a force of 0.01N by the pressurizer, it is heated from 20 ° C to 300 ° C at a temperature increase rate of 10 ° C / min. The bit start temperature is taken as the expansion start temperature (t).

The heat-expandable particles are preferably made of a thermoplastic resin, and a microencapsulated foaming agent composed of an encapsulated component, which is encapsulated outside, and is heated to a predetermined temperature.
Examples of the thermoplastic resin constituting the shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, poly Acrylonitrile, polyvinylidene chloride, polyfluorene, etc.

Inner components enclosed in the shell include, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane , Isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclo Tridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, neodecane, isotridecane, 4-methyldodecane, Isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isohexadecane, isooctadecane, isononanedecane, 2,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane , Pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane and the like.
These enclosed ingredients may be used alone or in combination of two or more.
The expansion start temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of the inclusion component.

The average particle diameter of the thermally expandable particles used in one aspect 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, and still more preferably 10 to 50 μm.
The average particle diameter before thermal expansion of the thermally expandable particles refers to the median diameter (D ₅₀ ), and a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name "Mastersizer 3000" is used). ”) The measured particle size distribution of the thermally expandable particles before expansion corresponds to a particle diameter with a cumulative volume frequency of 50% calculated from the smaller one of the thermally expandable particles before expansion.

The 90% particle diameter (D ₉₀ ) of the thermally expandable particles used in one aspect of the present invention before expansion at 23 ° C. is preferably 10 to 150 μm, more preferably 20 to 100 μm, and still more preferably 25 to 90 μm. It is preferably 30 to 80 μm.
The 90% particle size (D ₉₀ ) before the expansion of thermally expandable particles refers to the thermal expansion property before expansion measured using a laser diffraction particle size distribution measurement device (for example, manufactured by Malvern, product name "Mastersizer 3000"). The particle distribution of the particles corresponds to a particle diameter with a cumulative volume frequency of 90% calculated from the smaller of the particle diameters of the thermally expandable particles.

The maximum volume expansion rate when heated to a temperature above the expansion expansion temperature (t) of the thermally expandable particles used in one aspect of the present invention is preferably 1.5 to 100 times, more preferably 2 to 80 times, and even more preferably 2.5 to 60 times, and preferably 3 to 40 times.

<Thermally expandable base material layer (Y1-1)>
In the adhesive laminated body according to one aspect of the present invention, when the substrate (Y1) of the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles, the thermally expandable substrate layer (Y1) -1) It is preferable to satisfy the following requirement (1).
Requirements (1): The storage elastic modulus E '(t) of the thermally expandable base material layer (Y1-1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 × 10 ⁷ Pa or less.
In this specification, the storage elastic modulus E 'of the thermally expandable base material layer (Y1-1) at a predetermined temperature means a value measured by the method described in the examples.

The above-mentioned requirement (1) can be said to be an index indicating the rigidity of the thermally expandable base material layer (Y1-1) immediately before the thermally expandable particles are expanded.
Prior to the expansion of the heat-expandable particles, the storage elastic modulus E 'of the heat-expandable base material layer (Y1-1) decreases as the temperature increases. However, after reaching the expansion start temperature (t) of the thermally expandable particles, since the thermally expandable particles begin to expand, the decrease in the storage elastic modulus E 'of the thermally expandable substrate layer (Y1-1) is suppressed.
In addition, when the interface P of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) can be easily separated with a slight force, by heating to a temperature equal to or higher than the expansion start temperature (t), The surface on the side laminated with the base material (Y2) of the adhesive sheet (I) must be easy to form unevenness.
In other words, the thermally expandable base material layer (Y1-1) that satisfies the above-mentioned requirement (1) is based on the expansion start temperature (t), and the thermally expandable particles expand and become sufficiently large. It is easy to form unevenness | corrugation on the surface of the adhesive sheet (I) of the base material (Y2) laminated side.
As a result, at the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II), an adhesive laminate can be easily separated with a slight force.

The storage elastic modulus E '(t) defined by the requirements (1) of the thermally expandable substrate layer (Y1-1) used in the present invention is, in the above viewpoint, preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 × 10 ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.
In addition, the flow of the thermally expandable particles after expansion is suppressed, and the shape retention of the unevenness formed on the surface of the adhesive sheet (I) on the side laminated with the substrate (Y2) of the resin film forming sheet (II) is improved. The interface P is more easily separable from a slight force, and the storage elastic modulus E '(t) defined by the element (1) of the thermally expandable substrate layer (Y1-1) is preferably 1.0 × 10 ³ Pa or more. , More preferably 1.0 × 10 ⁴ Pa or more, and still more preferably 1.0 × 10 ⁵ Pa or more.

From the viewpoint of satisfying the thermally expandable substrate layer (Y1-1) of the above-mentioned requirement (1), the content of the thermally expandable particles in the thermally expandable substrate layer (Y1-1) is relative to the thermally expandable substrate layer (Y1-1). ) Of the total mass (100% by mass), preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass.

From the viewpoint of improving the interlayer adhesion with other layers laminated with the thermally expandable base material layer (Y1-1), the surface of the thermally expandable base material layer (Y1-1) may be subjected to an oxidation method or unevenness. Surface treatment, such as chemical treatment, easy subsequent treatment, or plasma treatment.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet type), hot air treatment, ozone and ultraviolet irradiation treatment, and examples of the unevenness method include sandblasting, solvent treatment, and the like.

The thermally expandable base material layer (Y1-1) is preferably formed of a resin composition (y) containing a resin and thermally expandable particles.
In addition, the resin composition (y) may contain an additive for a base material, if necessary, as long as the effect of the present invention is not impaired.
Examples of the additives for the substrate include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-blocking agents, and colorants.
Each of these base material additives may be used alone, or two or more of them may be used in combination.
When these base material additives are contained, the content of the respective base material additives is preferably 0.0001 to 20 parts by mass, and more preferably 0.001 to 10 parts by mass based on 100 parts by mass of the resin.

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

The resin contained in the resin composition (y) of the material for forming the thermally expandable base material layer (Y1-1) may be a non-adhesive resin or an adhesive resin.
In other words, even if the resin contained in the resin composition (y) is an adhesive resin, during the process of forming the thermally expandable base material layer (Y1-1) from the resin composition (y), the adhesive resin and the polymerizable compound are generated. In the polymerization reaction, the obtained resin may be a non-adhesive resin, and the thermally expandable base material layer (Y1-1) containing the resin may be non-adhesive.

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

The content of the resin is relative to the total amount (100% by mass) of the effective ingredients of the resin composition (y), preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and even more preferably 65 to 90% by mass , And preferably 70 to 85% by mass.

From the viewpoint of forming a thermally expandable base material layer (Y1-1) that satisfies the requirement (1), the resin system contained in the resin composition (y) contains a resin selected from an acrylic urethane resin and an olefin resin. One or more resins are preferred.
The acrylic urethane resin is preferably the following resin (U1).
An acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylate.

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

Examples of the polyol used as a raw material of the urethane prepolymer (UP) include an alkylene polyol, an ether polyol, an ester polyol, an ester-amine polyol, and an ester-ether ether polyol. Alcohols, carbonate-type polyols, and the like.
These polyols may be used alone or in combination of two or more kinds.
The polyol used in one aspect of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol and a carbonate diol. Diol.

Examples of the ester-type diol include an alkanediol selected from 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Ethylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc .; 1 or 2 or more types of glycols, and selected from the group consisting of 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, chlorobridged acid, horse Maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydrate One or two or more polycondensates of dicarboxylic acids such as hydrogenated terephthalic acid and methylhexahydrophthalic acid and the anhydrides thereof.
Specific examples include polyethylene adipate diol, polybutene adipate diol, polyhexamethylene adipate diol, and polyhexamethylene isophthalate diol. , Neopentyl adipate diol, polyethylene propylene adipate diol, polyvinyl butene adipate diol, polybutene hexamethylene adipate diol, polydiethylene Adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentyl adipate) diol, polyvinyl azelate diol , Polyethylene sebacate diol, polybutene azelate diol, polybutene sebacate diol, and poly neopentyl terephthalate diol.

Examples of the alkylene glycol include alkylene glycols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Ethylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polytetramethylene glycol, etc. Polyoxyalkylene glycol; etc.

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, 1,3-propylene carbonate diol, 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octa Methyl carbonate diol, 1,4-cyclohexane carbonate diol, and the like.

Examples of the polyvalent isocyanate used as a raw material of the urethane prepolymer (UP) include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.
These polyvalent isocyanates may be used alone or in combination of two or more kinds.
In addition, these polyvalent isocyanates may be trimethylolpropane addition-shaped modifiers, biuret-type modifiers that react with water, and trimeric isocyanate-type modifiers containing a trimeric isocyanate ring.

Among these, the polyvalent isocyanate used in one aspect of the present invention is preferably a diisocyanate, and more preferably selected from 4,4'-diphenylmethane diisocyanate (MDI) and 2,4-methylene benzene. One or more of a diisocyanate (2,4-TDI), a 2,6-methylenephenyl diisocyanate (2,6-TDI), a hexamethylene diisocyanate (HMDI), and an alicyclic diisocyanate.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., preferably isophor Ketone diisocyanate (IPDI).

In one aspect of the present invention, a reaction product of a urethane prepolymer (UP) diol and a diisocyanate, which becomes the main chain of an acrylic urethane resin (U1), has ethylene at both ends. A linear unsaturated urethane prepolymer having a preferable unsaturated group is preferred.
Examples of the method for introducing an ethylenically unsaturated group at both ends of the linear urethane prepolymer include a terminal of a linear urethane prepolymer obtained by reacting a diol with a diisocyanate compound. Method for reacting NCO group with hydroxyalkyl (meth) acrylate.

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

The vinyl compound that becomes the side chain of the acrylic urethane-based resin (U1) contains at least a (meth) acrylate.
The (meth) acrylate is preferably one or more selected from the group consisting of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate, and more preferably a combination of alkyl (meth) acrylate and hydroxyalkyl (Meth) acrylate.

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

The carbon number of the alkyl group in the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.

The hydroxyalkyl (meth) acrylate is the same as the hydroxyalkyl (meth) acrylate used to introduce an ethylenically unsaturated group at both ends of the linear urethane prepolymer. .

Examples of vinyl compounds other than (meth) acrylates include aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; and ethylene such as methyl vinyl ether and ethyl vinyl ether. Ethers; vinyl acetate, vinyl propionate, (meth) acrylonitrile, N-vinyl pyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, methyl (acrylamide) Etc. The polar group contains a monomer; etc.
These can be used alone or in combination of two or more.

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

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

The acrylic urethane resin (U1) used in one aspect of the present invention is obtained by mixing a urethane prepolymer (UP) with a vinyl compound containing a (meth) acrylate. The two are obtained by polymerization.
It is preferred to add a radical initiator to carry out the polymerization.

Among the acrylic urethane resin (U1) used in one aspect of the present invention, the constituent unit (u11) derived from the urethane prepolymer (UP) and the constituent unit (u12) derived from the vinyl compound The content ratio [(u11) / (u12)] is based on mass ratio, preferably 10/90 ~ 80/20, more preferably 20/80 ~ 70/30, and even more preferably 30/70 ~ 60/40 , And preferably 35/65 ~ 55/45.

(Olefin resin)
The resin contained in the resin composition (y) is preferably an olefin-based resin, for example, a polymer having at least a constituent 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, butene, diisobutylene, and 1-hexene.
Among these, ethylene and propylene are preferred.

The specific olefin-based resins such as very low density polyethylene (the VLDPE, density: 880kg / m ³ or more less than 910kg / m ^3), low density polyethylene (LDPE, density: 910kg / m ³ or more less than 915kg / m ³ ), medium density polyethylene (MDPE, density: 915kg / m ³ or more but less than 942kg / m ³ ), high density polyethylene (HDPE, density: 942kg / m ³ or more), linear low density polyethylene, etc. Polyethylene resin; 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 terpolymers such as ethylene-propylene- (5-ethylidene-2-norbene); etc.

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

For example, the acid-modified olefin-based resin obtained by subjecting the olefin-based resin to acid modification includes modified polymerization in which unsaturated carboxylic acid or its anhydride is graft-polymerized with the non-modified olefin-based resin described above. Thing.
Examples of the unsaturated carboxylic acid or its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, and (methyl). Acrylic acid, maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
The unsaturated carboxylic acid or its anhydride may be used singly or in combination of two or more kinds.

Examples of the acrylic modified olefin resin obtained by modifying acrylic resin with olefin resin include graft polymerization of an alkyl (meth) acrylate as a side chain and the non-modified olefin tree of the main chain. Modified polymer.
The carbon number of the alkyl group in the alkyl (meth) acrylate is preferably from 1 to 20, more preferably from 1 to 16, and even more preferably from 1 to 12.
Examples of the alkyl (meth) acrylate include the same compounds as those selectable as the monomer (a1 ′) described later.

Examples of the hydroxy-modified olefin-based resin obtained by subjecting the olefin-based resin to hydroxyl modification include modified polymers obtained by graft-polymerizing a hydroxyl-containing compound with the above-mentioned non-modified olefin-based resin in the main chain.
Examples of the hydroxyl-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylates, hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; vinyl alcohol, allyl Unsaturated alcohols such as alcohols.

(Resins 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 effect of the present invention is not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate Polyester resins such as diesters; polystyrene; acrylonitrile-butadiene-styrene copolymers; cellulose triacetate; polycarbonate; polyurethanes not equivalent to acrylic urethane resins Acid esters; polyfluorene; polyetheretherketone; polyetherfluorene; polyphenylene sulfide; polyetherimine resins such as polyimide, polyimide, etc. Resin, etc.

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

(Solvent-free resin composition (y1))
One aspect of the resin composition (y) used in one aspect of the present invention includes an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer, A solvent-free resin composition (y1) prepared by blending the above-mentioned thermally expandable particles without adding a solvent.
Although no solvent is added to the solvent-free resin composition (y1), the energy ray polymerizable monomer is one that contributes to improving the plasticity of the oligomer.
With respect to the coating film formed of the solventless resin composition (y1), a heat-expandable base material layer (Y1-1) that satisfies the above-mentioned requirement (1) can be easily formed by irradiating energy rays.

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

The mass average molecular weight (Mw) of the aforementioned oligomer contained in the solventless resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and even more preferably 3,000 to 35,000, It is preferably 4,000 to 30,000.

The oligomer may be any one of the resins contained in the resin composition (y) and has an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less. The urethane prepolymer is preferable.物 (UP).
As the oligomer, a modified olefin-based resin having an ethylenically unsaturated group may be used.

In the solventless resin composition (y1), the total content of the aforementioned oligomer and energy ray polymerizable monomer is relative to the total amount (100% by mass) of the solventless resin composition (y1), and is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass.

Examples of the energy ray polymerizable monomer include isofluorenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, and dicyclopentenyloxy ( Alicyclic polymerizable compounds such as meth) acrylate, cyclohexyl (meth) acrylate, adamantane (meth) acrylate, tricyclodecane acrylate; phenylhydroxypropyl acrylate, benzyl acrylic acid Aromatic polymerizable compounds such as esters, phenol ethylene oxide modified acrylates; tetrahydrofurfuryl (meth) acrylates, morpholine acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, etc. Heterocyclic polymerizable compounds and the like.
These energy ray polymerizable monomers may be used alone or in combination of two or more kinds.

In the solventless resin composition (y1), the content ratio of the oligomer to the energy ray polymerizable monomer [oligomer / energy ray polymerizable monomer] is a mass ratio, preferably 20/80 ~ 90/10, more preferably 30/70 ~ 85/15, and even more preferably 35/65 ~ 80/20.

In one aspect of the present invention, a solvent-free resin composition (y1) is further preferably prepared by further blending a photopolymerization initiator.
Since the photopolymerization initiator is contained, a sufficiently hardening reaction can be performed even by irradiation with a relatively low energy energy ray.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, Methylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, diethylfluorenyl, 8-chloroanthraquinone, etc.
These photopolymerization initiators may be used alone or in combination of two or more kinds.

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 more than the total amount (100 parts by mass) of the aforementioned oligomer and energy ray polymerizable monomer. It is preferably 0.02 to 3 parts by mass.

<Non-thermally expandable base material layer (Y1-2)>
The material for forming the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) may be, for example, paper, resin, metal, etc., and the application of the adhesive laminate according to one aspect of the present invention may be appropriately selected. .

Examples of the paper material include thin-leaf paper, medium-quality paper, high-quality paper, impregnated paper, cast-coated paper, art paper, sulfuric acid paper, and cellophane.
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 ; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; three Cellulose acetate; polycarbonate; polyurethane resins such as polyurethane, acryl fluorenyl modified polyurethane, etc .; polymethylpentene; polyfluorene; polyether ether ketone; poly Ethers; Polyphenylene sulfide; Polyethers, imines, polyimides, and other polyimide-based resins; polyimide-based resins; acrylic resins; fluorine-based resins.
Examples of the metal include aluminum, tin, chromium, and titanium.

These forming materials may be composed of one type, or two or more types may be used in combination.
Examples of the non-thermally expandable base material layer (Y1-2) that uses two or more types of forming materials include a paper material laminated with a thermoplastic resin such as polyethylene, or a resin film or sheet containing a resin with a metal film formed on the surface. Wait.
The method for forming the metal layer includes, for example, a method in which the above-mentioned metal is vapor-deposited by a PVD method such as vacuum deposition, sputtering, and ion plating, or a metal foil made of the above-mentioned metal is stuck using a general adhesive. Methods etc.

From the viewpoint of improving the interlayer adhesion with the other layers laminated with the non-thermally expandable base material layer (Y1-2), when the non-thermally expandable base material layer (Y1-2) contains a resin, The surface of the layer (Y1-2) may be subjected to a surface treatment by an oxidation method, an unevenness method, or the like, as well as a plasma treatment, similarly to the thermally expandable substrate layer (Y1-1).

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

The non-thermally expandable base material layer (Y1-2) is a non-thermally expandable layer judged according to the method described above.
Therefore, the volume change rate (%) of the non-thermally expandable substrate layer (Y1-2) calculated from the above formula is less than 5%, preferably less than 2%, more preferably less than 1%, and more preferably It is 0.1%, and preferably less than 0.01%.

When the volume change rate of the non-thermally expandable base material layer (Y1-2) is in the above range, heat-expandable particles may be contained. For example, by selecting the resin contained in the non-thermally expandable base material layer (Y1-2), the volume change rate can be adjusted to the above range even if the thermally expandable particles are included.
However, the smaller the content of the thermally expandable particles in the non-thermally expandable substrate layer (Y1-2), the better.
The content of specific heat-expandable particles is relative to the total mass (100% by mass) of the non-thermal-expandable substrate layer (Y1-2), which is usually less than 3% by mass, preferably less than 1% by mass, and more preferably 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.

＜ Adhesive layer (X1) ＞
The adhesive layer (X1) included in the adhesive sheet (I) used in one aspect of the present invention may be formed of an adhesive composition (x1) containing an adhesive resin.
Moreover, the adhesive composition (x1) may contain additives for adhesives, such as a crosslinking agent, an adhesion-imparting agent, a polymerizable compound, a polymerization initiator, etc. as needed.
Hereinafter, each component contained in the adhesive composition (x1) will be described.
When the adhesive sheet (I) has the first adhesive layer (X11) and the second adhesive layer (X12), the first adhesive layer (X11) and the second adhesive layer (X12) may include the following: The adhesive composition (x1) of each component shown is formed.

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

Specific adhesive resins include, for example, rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, polysiloxane-based resins, and polyvinyl ether-based resins. Resin, etc.
These adhesive resins can be used alone or in combination of two or more.
When the adhesive resin is a copolymer having two or more kinds of constituent units, the form of the copolymer is not particularly limited, and the copolymer may be any of a segment copolymer, a random copolymer, and a graft copolymer. One.

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

In one aspect of the present invention, the adhesive resin preferably includes an acrylic resin from the viewpoint of exhibiting excellent adhesion.
When an adhesive sheet (I) having a first adhesive layer (X11) and a second adhesive layer (X12) is used, the first adhesive layer (X11) comes into contact with the resin film-forming sheet (II). ) Contains an acrylic resin and can easily form irregularities on the surface of the first adhesive layer.

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

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

The mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1.5 million, more preferably 200,000 to 1.3 million, still more preferably 350,000 to 1.2 million, and still more preferably 500,000 to 1.1 million.

The acrylic resin used in one aspect of the present invention preferably has a constituent unit (p1) derived from an alkyl (meth) acrylate (p1 ') (hereinafter also referred to as "monomer (p1')") and An acrylic copolymer (P) derived from a constituent unit (p2) of a functional group-containing monomer (p2 ') (hereinafter also referred to as "monomer (p2')").

The carbon number of the alkyl group in the monomer (p1 ') is preferably from 1 to 24, more preferably from 1 to 12, still more preferably from 2 to 10, and even more preferably from 4 to the viewpoint of improving the adhesion characteristics. 8.
The alkyl group of the monomer (p1 ′) may be a linear alkyl group or a branched alkyl group.

Examples of the monomer (p1 ') include meth (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (Meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, and the like.
These monomers (p1 ') may be used alone or in combination of two or more kinds.
The monomer (p1 ′) is preferably butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

The content of the constituent unit (p1) is relative to the total constituent unit (100% by mass) of the acrylic copolymer (P), preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, and even more preferably 70 ~ 97.0% by mass, and more preferably 80 ~ 95.0% by mass.

Examples of the functional group of the monomer (p2 ′) include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.
In other words, examples of the monomer (p2 ′) include a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, and a monomer containing an epoxy group.
These monomers (p2 ') may be used alone or in combination of two or more kinds.
Among these, the monomer (p2 ') is preferably a monomer containing a hydroxyl group and a monomer containing a carboxyl group.

Examples of the hydroxyl group-containing monomer include the same as the above-mentioned hydroxyl group-containing compound.

Examples of the carboxyl 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. Acids and their anhydrides, 2- (propenyloxy) ethylsuccinate, 2-carboxyethyl (meth) acrylate, and the like.

The content of the constituent unit (p2) is 0.1 to 40 mass%, more preferably 0.5 to 35 mass%, and even more preferably 1.0 relative to the total constituent unit (100% by mass) of the acrylic copolymer (P). ~ 30 mass%, and more preferably 3.0 to 25 mass%.

The acrylic copolymer (P) may further have a structural unit (p3) derived from a monomer (p3 ') other than the monomers (p1') and (p2 ').
In addition, the content of the constituent units (p1) and (p2) in the acrylic copolymer (P) is preferably 70 to 100% by mass relative to the total constituent unit (100% by mass) of the acrylic copolymer (P). It is more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 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; and diene systems such as butadiene, isoprene, and chloroprene. Monomers; cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isofluorenyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (methyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (imine) (meth) acrylate with a cyclic structure; styrene, α-methyl Styrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acrylfluorenylmorpholine, N-vinylpyrrolidone, and the like.

The acrylic copolymer (P) may be an energy ray-curable acrylic copolymer having a polymerizable functional group introduced into a side chain.
The polymerizable functional group and the energy ray system are as described above.
In addition, the polymerizable functional group may be bonded by an acrylic copolymer having the above-mentioned constituent units (p1) and (p2) and a functional group having a constituent unit (p2) which can be combined with the acrylic copolymer. The substituent is introduced by reacting with a compound of a polymerizable functional group.
Examples of the compound include (meth) acryloxyethyl isocyanate, (meth) acrylmethyl isocyanate, and glycidyl (meth) acrylate.

(Crosslinking agent)
In one aspect of the present invention, the adhesive composition (x1) is, for example, the acrylic copolymer (P) described above, and when the adhesive resin having a functional group is contained, it is preferable to further have a crosslinking agent.
This crosslinking agent reacts with an adhesive resin having a functional group, and uses the functional group as a starting point for crosslinking, and the adhesive resins are crosslinked with each other.

Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an aziridine-based crosslinking agent, and a metal chelate-based crosslinking agent.
These crosslinking agents may be used alone or in combination of two or more kinds.
Among these cross-linking agents, an isocyanate-based cross-linking agent is preferred from the viewpoints of improving cohesion, improving adhesion, and ease of obtaining.

The content of the cross-linking agent is appropriately adjusted by the number of functional groups of the adhesive resin, and is preferably 0.01 to 10 parts by mass, and more preferably 0.03 to 7 relative to 100 parts by mass of the adhesive resin having functional groups. Mass parts, and more preferably 0.05 to 5 parts by mass.

(Adhesion imparting agent)
In one aspect of the present invention, the adhesive composition (x1) may further improve the adhesion, and may further include an adhesion-imparting agent.
In this specification, an "adhesion imparting agent" is a component which supplementally improves the adhesive force of the said adhesive resin, and means the oligomer whose mass average molecular weight (Mw) is less than 10,000, and is different from the said adhesive resin.
The mass average molecular weight (Mw) of the adhesion imparting agent is preferably 400 to 10,000, more preferably 500 to 8000, and still more preferably 800 to 5000.

Examples of the adhesion-imparting agent include C5 retention of rosin-based resins, terpene-based resins, styrene-based resins, and pentene produced by thermal decomposition of petroleum brain, isoprene, piperine, and 1,3-pentadiene. C5 based petroleum resins obtained by sub-copolymerization, C9 based petroleum resins obtained by in-situ copolymerization of C9 residues such as indene, vinyltoluene, etc. produced by thermal decomposition of petroleum brain, and hydrogenated resins which are hydrogenated.

The softening point of the adhesion imparting agent is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and even more preferably 70 to 150 ° C.
In this specification, the "softening point" of the adhesion-imparting agent means a value measured in accordance with JIS K 2531.
The adhesion-imparting agent may be used alone or in combination of two or more different softening points or different structures.
In addition, when two or more plural types of adhesion-imparting agents are used, it is preferable that the weighted average of the softening points of the plural adhesion-imparting agents belong to the above range.

The content of the adhesion-imparting agent is relative to the total amount (100% by mass) of the active ingredient of the adhesive composition (x1) or the total mass (100% by mass) of the adhesive layer (X1), preferably 0.01 to 65% by mass. It is more preferably 0.05 to 55 mass%, still more preferably 0.1 to 50 mass%, still more preferably 0.5 to 45 mass%, and still more preferably 1.0 to 40 mass%.

(Photopolymerization initiator)
In one aspect of the present invention, when the adhesive composition (x1) includes an energy ray-curable adhesive resin as an adhesive resin, it is preferable to further include a photopolymerization initiator.
By containing a photopolymerization initiator, a sufficiently hardening reaction can be performed even by irradiation with a relatively low energy energy ray.
Examples of the photopolymerization initiator include the same as those formulated for the solventless resin composition (y1).

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 still more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the energy ray-curable adhesive resin.

(Additives for adhesives)
In one aspect of the present invention, the adhesive composition (x1) may contain, in addition to the above-mentioned additives, an additive for an adhesive used in a general adhesive, as long as the effect of the present invention is not impaired.
Examples of such additives for adhesives include antioxidants, softeners (plasticizers), mothproofing agents, pigments, dyes, retarders, reaction accelerators (catalysts), and ultraviolet absorbers.
These additives for adhesives may be used singly or in combination of two or more kinds.

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

When the adhesive sheet (I) of the second aspect is used in the adhesive laminate 2 shown in FIG. 3, the first adhesive layer (X11) of the thermally expandable adhesive layer is further composed of thermally expandable particles. It is formed by the thermally expandable adhesive composition (x11).
The thermally expandable particles are as described above.
The content of the heat-expandable particles is preferably 1 to 70% by mass based on the total amount (100% by mass) of the active ingredient of the thermally expandable adhesive composition (x11) or the total mass (100% by mass) of the thermally expandable adhesive layer. , More preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and even more preferably 5 to 40% by mass.

In addition, when the adhesive layer (X1) is a non-thermally expandable adhesive layer, the content of the thermally expandable particles in the non-thermally expandable adhesive composition of the material forming the non-thermally expandable adhesive layer is preferably as small as possible.
The content of the thermally expandable particles is based on the total amount (100% by mass) of the active ingredient of the non-thermally expandable adhesive composition or the total mass (100% by mass) of the non-thermally expandable adhesive layer, preferably less than 1% by mass. More preferably, it is less than 0.1 mass%, still more preferably it is less than 0.01 mass%, and even more preferably it is less than 0.001 mass%.

When the adhesive laminates 1c and 1d shown in FIG. 2 use the adhesive sheet (I) of the first adhesive layer (X11) and the second adhesive layer (X12) having a non-thermally expandable adhesive layer, The storage shear modulus G '(23) of the first adhesive layer (X11) of the non-thermally expandable adhesive layer at 23 ° C is preferably 1.0 × 10 ⁸ Pa or less, and more preferably 5.0 × 10 ⁷ Pa or less, and more preferably 1.0 × 10 ⁷ Pa or less.
When the shear storage modulus G '(23) of the first adhesive layer (X11) of the non-thermally expandable adhesive layer is 1.0 × 10 ⁸ Pa or less, for example, the adhesive laminates 1c and 1d shown in FIG. 2 In the constitution, the first adhesive layer (X11) is in contact with the resin film forming sheet (II) by expansion of the thermally expandable particles in the thermally expandable substrate layer (Y1-1) for heat treatment for separation. The surface is prone to unevenness. As a result, an adhesive laminated body that can be easily separated at a time with a slight force at the interface P of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) can be formed.
The shear storage modulus G '(23) of the first adhesive layer (X11) of the non-thermally expandable adhesive layer at 23 ° C is preferably 1.0 × 10 ⁴ Pa or more, and more preferably 5.0 × 10 ⁴ Pa or more, and more preferably 1.0 × 10 ⁵ Pa or more.

[Configuration of Resin Film Forming Sheet (II)]
In the adhesive laminated body of the present invention, the sheet (II) for forming a resin film has a curable resin layer (Z2) on one surface side of the substrate (Y2), and is adhered on the other surface side of the substrate (Y2) Sheet (I) is directly laminated.
Moreover, in the adhesive laminated body which concerns on one aspect of this invention, the sheet (II) for resin film formation may have an adhesive layer (X2) between a base material (Y2) and a curable resin layer (Z2).

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

＜ Base material (Y2) ＞
The material for forming the base material (Y2) may be the same as the material for forming the non-thermally expandable base material layer (Y1-2).
The substrate (Y2) preferably contains a resin, and it is more preferable to form a resin-containing resin layer on at least the surface of the substrate (Y2) laminated with the adhesive sheet (I). The substrate (Y2) is a resin film or a resin sheet. Even better.
In addition, after the heat treatment for separation, from the viewpoint that the interface P can be easily separated at a time with a slight force, the surface of the laminated layer side of the adhesive sheet (I) of the substrate (Y2) is preferably subjected to a peeling treatment. s surface.

In addition, it is easy to prevent the positional deviation of a processing object such as a semiconductor wafer when it is adhered to the curable resin layer (Z2), and it is easy to prevent the process object from being excessively sunk into the curable resin layer (Z2) when the object is adhered when heating. From the viewpoint of), the storage elastic modulus E '(23) at 23 ° C of the base material (Y2) is preferably 1.0 × 10 ⁶ Pa or more.

In addition, when the volume change rate of the base material (Y2) is within the above range, it may have heat-expandable particles, but from the above viewpoint, the content of the heat-expandable particles in the base material (Y2) is preferably as small as possible.
The content of the thermally expandable particles in the substrate (Y2) is relative to the total mass (100% by mass) of the substrate (Y2), which is usually less than 3% by mass, preferably less than 1% by mass, and more preferably It is 0.1% by mass, more preferably 0.01% by mass, and still more preferably 0.001% by mass.

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

<Curable resin layer (Z2)>
The hardenable resin layer (Z2) may be formed of a composition that hardens to form a hardenable resin film, but is preferably a hardenable composition (z) containing a polymer component (A) and a hardenable component (B). ).
The curable composition (z) may further contain one or more selected from the group consisting of a colorant (C), a coupling agent (D), and an inorganic filler (E).
The curable composition (z) may further contain a cross-linking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion trapping agent, a gettering agent, and the like within a range that does not impair the effects of the present invention. Additives such as chain transfer agents.
The components (A) to (F) contained in the curable composition (z) of the material for forming the curable resin layer (Z2) will be described below.

(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), it is possible to impart flexibility and film-forming properties to the curable resin layer (Z2), and it is possible to maintain good sheet properties.
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, and still more preferably 100,000 to 1.5 million. More preferably, it is 200,000 to 1 million.

The content of the component (A) is based on the total amount (100% by mass) of the effective component of the curable composition (z) or the total mass (100% by mass) of the curable resin layer (Z2), and is preferably 5 to 50%. %, 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 kinds.
Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, and rubber-based polymers.
In this specification, the acrylic polymer (A1) having an epoxy group or the phenoxy resin having an epoxy group has thermosetting properties, but when it corresponds to the "polymer component" described above, these are not hardening properties. The component (B) is a concept included in the polymer component (A).

Among these, the polymer component (A) preferably contains an acrylic polymer (A1).
The content of the acrylic polymer (A1) in the polymer component (A) is relative to the total amount (100% by mass) of the polymer component (A), preferably 60 to 100% by mass, and more preferably 70 to 100 Mass% is more preferably 80 to 100% by mass, and still 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, and more preferably 100,000 to the viewpoint of imparting flexibility and film-forming properties to the curable resin layer (Z2). 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 from the viewpoint of adhering to the adherend of the curable resin layer (Z2) and improving the resin attached using the sheet (II) for forming a resin film From the viewpoint of the reliability of the processing object of the film, it is preferably -60 to 50 ° C, more preferably -50 to 30 ° C, still more preferably -40 to 10 ° C, and still more preferably -35 to 5 ° C.

Examples of the acrylic polymer (A1) include a polymer containing an alkyl (meth) acrylate as a main component, and specifically, it is preferable to include an alkyl (methyl) derived from an alkyl group having 1 to 18 carbon atoms. The acrylic polymer containing the structural unit (a1) of acrylate (a1 ') (hereinafter also referred to as "monomer (a1')") preferably contains a monomer derived from the structural unit (a1) and a functional group (a a2 ') (hereinafter also referred to as "monomer (a2')") is an acrylic copolymer of a constituent unit (a2).
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 interactive copolymer, and a graft copolymer.

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

From the viewpoint of improving the reliability of the object to be processed with the resin film produced by using the resin film-forming sheet (II), the monomer (a1 ') includes an alkyl group (a) having an alkyl group having 1 to 3 carbon atoms. (Meth) acrylate is more preferred, and meth (meth) acrylate is more preferred.
From the above point of view, the content of the constituent unit (a11) of the alkyl (meth) acrylate derived from the alkyl group having 1 to 3 carbon atoms is based on the total constituent 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 even more preferably 10 to 80% by mass.

In addition, from the viewpoint of improving the glossiness of the resin film by using the resin film-forming sheet (II) and the object with the resin film to be processed, the monomer film (a1 ') is more suitable for laser printing. Preferably, it contains an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, more preferably it contains an alkyl (meth) acrylate having an alkyl group having 4 to 6 carbon atoms, and even more preferably contains butyl (Meth) acrylate.
From the above viewpoint, the content of the constituent unit (a12) of the alkyl (meth) acrylate derived from an alkyl group having a carbon number of 4 or more (preferably 4 to 6, and more preferably 4) is polymerized with respect to the acrylic system. The total constituent unit (100% by mass) of the substance (A1) is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and even more preferably 10 to 60% by mass.

The content of the constituent unit (a1) is relative to the total constituent unit (100% by mass) of the acrylic polymer (A1), preferably 50% by mass or more, more preferably 50 to 99% by mass, and even more preferably 55 to 90% by mass, and more preferably 60 to 90% by mass.

The monomer (a2 ') may be the same as the monomer (p2'), and is preferably one or more selected from the group consisting of a hydroxyl group-containing monomer and an epoxy group-containing monomer.
The monomer (a2 ') may be used alone or in combination of two or more kinds.

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

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (methyl (Meth) acrylate, 3-epoxycyclo-2-hydroxypropyl (meth) acrylate, etc. (meth) acrylates containing epoxy groups; glycidyl crotonate, allyl glycidyl ether Wait.
Among these, an epoxy group-containing (meth) acrylate is preferable, and a glycidyl (meth) acrylate is more preferable.

The content of the constituent unit (a2) is relative to the total constituent unit (100% by mass) of the acrylic polymer (A1), preferably 1 to 50% by mass, more preferably 5 to 45% by mass, and even more preferably 10 ~ 40% by mass, and even more preferably 10 ~ 30% by mass.

The acrylic polymer (A1) may contain a constituent unit derived from a monomer other than the constituent 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, and α-olefin.

<Sclerosing component (B)>
The curable component (B) is a compound that hardens the curable resin layer (Z2) to form a hard resin film, and has a mass average molecular weight of less than 20,000.
As the curable component (B), it is preferable to use a thermosetting component (B1) and / or an energy ray-curable component (B2). From the viewpoint of suppressing the coloring of the resin film formed by the curable resin layer (Z2), From the viewpoint of sufficiently progressing the curing reaction and the viewpoint of cost reduction, it is more preferable to use a thermosetting component (B1).

The thermosetting component (B1) is preferably a compound containing at least a functional group that reacts by heating.
In addition, the energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts by energy ray irradiation, and undergoes polymerization and hardening when irradiated with energy rays such as ultraviolet rays and electron beams.
The functional groups of these hardenable components react with each other to achieve hardening by forming a three-dimensional mesh structure.

When a thermosetting component (B1) is used, the formed curable resin layer (Z2) is heated at a temperature less than the thermal expansion start temperature (t) to cause hardening before the formed P is separated at the interface P.
When an energy ray-curable component (B2) is used, the formed curable resin layer (Z2) is hardened by applying energy irradiation instead of heat treatment.

The mass average molecular weight (Mw) of the curable component (B) is preferably used in combination with the component (A) to suppress the viscosity of the composition for forming the curable resin layer (Z2) and improve the workability. It is less than 20,000, more preferably less than 10,000, and even more preferably 100 to 10,000.

(Thermosetting component (B1))
The thermosetting component (B1) is preferably an epoxy-based thermosetting component.
The epoxy-based thermosetting component is preferably one using an epoxy compound (B11) and a thermosetting agent (B12) in combination with a compound having an epoxy group.

Examples of the epoxy compound (B11) include a polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydride, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, and biphenyl ring. Oxygen resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins, and the like have an epoxy compound having more than two functions and 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 kinds.

The content of the epoxy compound (B11) is based on 100 parts by mass of the component (A), preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, still more preferably 10 to 150 parts by mass, and even more It is preferably 20 to 120 parts by mass.

(Heat hardener (B12))
The thermal hardener (B12) functions as an epoxy compound (B11) as a hardener.
The thermosetting agent is a compound having two or more functional groups capable of reacting with epoxy groups in one molecule.
Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acid anhydride. Among these, a phenolic hydroxyl group, an amine group, or an acid anhydride is preferable, a phenolic hydroxyl group or an amine group is more preferable, and an amine group is more preferable.

Examples of the phenol-based thermosetting agent having a phenol group include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, Zilog-type phenol resins, and aralkylphenol resins. .
Examples of the amine-based thermosetting agent having an amine group include dicyandiamide (DICY).
These heat curing agents (B12) may be used alone or in combination of two or more kinds.

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 based on 100 parts by mass of the epoxy compound (B11).

(Hardening accelerator (B13))
In order to adjust the rate of thermal curing of the curable resin layer (Z2), a curing accelerator (B13) may be used. The hardening accelerator (B13) is preferably used in combination with an epoxy compound (B11) as a thermosetting component (B1).

Examples of the hardening accelerator (B13) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethyl imidazole; organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; etc .; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc. Tetraphenylboron salt, etc.
These hardening accelerators (B13) can be used alone or in combination of two or more.

The content of the hardening accelerator (B13) is from the viewpoint of improving the adhesiveness of the hardening resin layer (Z2), and from the viewpoint of improving the reliability of the object to be processed with the resin film produced by using the resin film forming sheet (II). Relative to 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12), preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and even more preferably 0.3 to 4 parts by mass .

(Energy ray hardening component (B2))
As the energy ray-curable component (B2), a compound (B21) having a functional group that generates a reaction upon irradiation with energy ray can be used alone, but a combination of the compound (B21) and a photopolymerization initiator (B22) is preferably used.

(Compound (B21) having a functional group that reacts by irradiation with energy rays)
Examples of the compound (B21) (hereinafter also referred to as "energy-ray-reactive compound (B21)") having a functional group that causes a reaction upon irradiation with energy rays include trimethylolpropane triacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, oligoester acrylate, amino formic acid Ester acrylate oligomers, epoxy acrylates, polyether acrylates, itaconic acid oligomers, and the like.
These energy ray reactive compounds (B21) may be used alone or in combination of two or more kinds.
The mass average molecular weight (Mw) of the energy ray-reactive compound (B21) is preferably 100 to 30,000, and 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 based on 100 parts by mass of the component (A).

(Photopolymerization initiator (B22))
By using the energy ray reactive compound (B21) and the photopolymerization initiator (B22) in combination, the curing time can be shortened, and the curable resin layer (Z2) can be cured even with a small amount of light exposure.
Examples of the photopolymerization initiator (B22) are the same as those prepared for the solventless resin composition (y1).
The content of the photopolymerization initiator (B22) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the energy ray-reactive compound (B21) from the viewpoint of sufficiently progressing the curing reaction and suppressing the formation of residues. More preferably, it is 1 to 5 parts by mass.

The content of the component (B) is based on the total amount (100% by mass) of the curable resin layer (Z2), preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 30% by mass. %, And even more preferably 12 to 25% by mass.
The content of the component (B) is a thermosetting component (B1) containing the epoxy compound (B11), a thermosetting agent (B12), and a hardening accelerator (B13), and an energy ray-reactive compound (B21). ), And the total content of the energy ray-curable component (B2) of the photopolymerization initiator (B22).

<Colorant (C)>
The curable resin layer (Z2) preferably further contains a colorant (C).
A process object having a resin film formed from the hardening resin layer (Z2) by containing the colorant (C) in the hardening resin layer (Z2), for example, when a semiconductor wafer having a resin film is assembled in a machine, it is shielded. Infrared rays generated by surrounding devices can prevent malfunction of the semiconductor wafer.

As the colorant (C), organic or inorganic pigments and dyes can be used.
As the dye, for example, any of 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 a known pigment can be appropriately selected and used.
Among these, black pigments are preferred from the viewpoints of good shielding properties of electromagnetic waves and infrared rays, and more improved visibility by the laser printing method.
Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon. From the viewpoint of improving the reliability of a semiconductor wafer, carbon black is preferred.
These coloring agents (C) may be used alone or in combination of two or more kinds.

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

＜ Coupling agent (D) ＞
It is preferable that the curable resin layer (Z2) further contains a coupling agent (D).
By including 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 wafer or the surface of the filler, thereby improving adhesion and cohesiveness. Moreover, without impairing the heat resistance of the resin film formed by the curable resin layer (Z2), the water resistance can be improved.

The coupling agent (D) is preferably a compound that reacts with a functional group of the component (A) or the component (B), and more preferably a silane coupling agent.
Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl ) Ethyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-amine Propyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ -Ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide Hydrogen, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane, and the like.
These (D) coupling agents may be used alone or in combination of two or more kinds.

The coupling agent (D) is preferably an oligomeric coupling agent.
The molecular weight of the coupling agent (D), which is also included in the oligomeric coupling agent, is preferably 100 to 15,000, more preferably 150 to 10,000, more preferably 200 to 5000, still more preferably 250 to 3000, and even more It is preferably 350 ~ 2000.

The content of the component (D) is relative to the total amount (100% by mass) of the curable resin layer (Z2), preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, and still more preferably 0.10 to 4% by mass %, And even 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), the thermal expansion coefficient of the cured resin film of the curable resin layer (Z2) can be adjusted to a suitable range, and for a processing object such as a semiconductor wafer, the cured resin film can be adjusted The thermal expansion coefficient is optimized to include a resin film formed from a curable resin layer (Z2) and a product to be processed. For example, when the object to be processed is a semiconductor wafer, the reliability of the semiconductor wafer can be improved. In addition, the moisture absorption of the cured resin film can be reduced.

As long as the inorganic filler (E) is non-thermally expandable, examples thereof include powders of silicon dioxide, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, and the like. Non-thermally expandable 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, silicon dioxide or aluminum oxide is preferred.

The average particle diameter of the inorganic filler (E) is preferably 0.3 to 50 μm from the viewpoint of improving the gloss of the resin film of the object to be processed with the resin film produced by using the resin film forming sheet (II). It is preferably 0.5 to 30 μm, and more preferably 0.7 to 10 μm.

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

＜ Adhesive layer (X2) ＞
The adhesive layer (X2) included in the resin film-forming sheet (II) can be formed using the above-mentioned adhesive composition (x1), and a preferable component or a preferable range of the content of each component is also the same as the adhesive composition (x1). )the same.

After the curable resin layer (Z2) is cured to form a cured resin film, layers other than the curable resin layer (Z2) of the resin film-forming sheet (II) are removed.
Therefore, the adhesive layer (X2) has good interlayer adhesion with the hardening resin layer (Z2) before curing, and it is preferable that the hardening resin layer (Z2) is adjusted to be easily peelable after curing to form a hardened resin film.
From the above viewpoint, it is preferable that the adhesive composition of the material for forming the adhesive layer (X2) is an energy-ray-curable adhesive resin containing, as an adhesive resin, a polymerizable functional group introduced into a side chain.

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

＜ Peeling material ＞
In one aspect of the present invention, the adhesive laminated system can further be laminated on the surface of the adhesive layer (X1) and the hardening resin layer (X2) adhered to the adherend.
As the release material, a release sheet having a release treatment on both sides or a release sheet having a release treatment on one side can be used, and examples thereof include a case where a release agent is applied to a substrate for the release material.

Examples of the base material for the release material include papers such as high-quality paper, cellophane, and kraft paper; polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and the like Polyester resin film, polypropylene resin, polyethylene resin, olefin resin film, etc. plastic film; etc.

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

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

[Manufacturing method of processing object with resin film]
The adhesive lamination system of the present invention fixes an object to be processed to a support, and can perform predetermined processing. At the same time, after processing, it can be easily separated from the support only once with a slight force. After separation, a hardened resin film can be obtained. Object with resin film.
Therefore, by using the adhesive laminated body of the present invention, the following operations can be performed at one time, and productivity can be expected to be improved, that is, in order to fix the processing object to the support before processing, the adhesive sheet is adhered to the processing object. After the work and processing, the work of removing the adhesive sheet from the object to be processed and pasting the sheet for forming a resin film is performed.

A more specific method for producing the object to be processed with a resin film includes a method having the following steps (α-1) to (α-3).
Step (α-1): The surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate is adhered to the support, and at the same time, the curable resin layer (II) of the resin film forming sheet (II) ( Z2) The step of placing or adhering the processing object on the surface,
Step (α-2): a step of performing a specific processing on the aforementioned processing object,
Step (α-3): A separation occurs at the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) by heating above the thermal expansion start temperature (t) of the thermally expandable particles. , A step of obtaining a processing object with a resin film.

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

<Step (α-1)>
Step (α-1) is to adhere the surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate to the support, and at the same time, to the curable resin layer (II) of the resin film-forming sheet (II) ( Z2) A step of placing or adhering a processing object on a surface.
FIG. 4 (a) is a schematic cross-sectional view showing a state where a processing object is fixed to a support via the adhesive laminated body 1a of the first aspect of the present invention shown in FIG. 1 (a).
In step (α-1), as shown in FIG. 4 (a), the processing object 60 is fixed to the support body 50 via the adhesive laminated body 1 a of the first aspect of the present invention, and the support body and the adhesion body are adhered according to the aforementioned support body and the aforementioned adhesion body. The laminated body and the object to be processed and inspected are laminated in this order.
Fig. 4 shows an example of using the adhesive laminated body 1a shown in Fig. 1 (a). However, when the adhesive laminated body of the present invention having another structure is used, the support and the adhesive are similarly applied in the same manner. The laminated body and the object to be processed and inspected are laminated in this order.

Examples of the processing target to which the adhesive laminated body is adhered include a semiconductor wafer, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, and a panel substrate.

In the step (α-2), the aforementioned support system is used to fix the object to be processed and improve the processing accuracy.
The aforementioned support is preferably the entire surface of the adhesive surface of the adhesive layer (X1) adhered to the adhesive laminate.
Therefore, the support system is preferably a plate. In addition, the area of the surface of the support on the side of the adhesive surface to the adhesive surface of the adhesive layer (X1) is shown in FIG. 4, and is preferably greater than the area of the adhesive surface of the adhesive layer (X1).

The material constituting the support is appropriately selected depending on the type of the object to be processed or the processing applied in step (α-2), taking into consideration required characteristics such as mechanical strength and heat resistance.
The material constituting the specific support body can be exemplified by metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic ( super engineering plastics), polyimide resins, polyimide resins, etc .; composite materials such as glass epoxy resins, among these, SUS, glass, and silicon wafers are preferred .
Examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether fluorene (PES), and polyether ether ketone (PEEK).

The thickness of the support is appropriately selected in consideration of the processing type and the like in the next step, and 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 step (α-1) may be any temperature that does not reach the expansion start temperature (t) of the thermally expandable particles, but in an environment of 0 to 80 ° C (the expansion start temperature (t) is 60 to 80) At ℃, it is better to perform under an environment where the expansion start temperature (t) is not reached.

＜ Step (α-2) ＞
Step (α-2) is a step of performing a predetermined processing on the object to be processed, which is adhered to the curable resin layer (Z2) of the adhesive laminate of the present invention in step (α-1).
The processing performed in step (α-2) includes, for example, a packaging process for an object using a resin, a grinding process for the object, a cutting (piece-forming) process, a circuit formation process, an etching process, a plating process, and a sputtering process. A plating process, a vapor deposition process, and a lamination process using the prepared adhesive sheet separately.
In addition, this step (α-2) may be performed by a combination of two or more of these processes.

The temperature condition in step (α-2) is preferably performed under a temperature environment that does not reach the expansion start temperature (t) of the thermally expandable particles.
In step (α-2), the hardening resin layer (Z2) may be hardened to form a hardened resin film in parallel with the above-mentioned processing. For example, when the processing performed in this step is a process accompanied by heating, the curable resin layer (Z2) is hardened by the heat to form a cured resin film.

In addition, when the step (α-2) is processed, if the hardening resin layer (Z2) is not cured, if necessary, after step (α-2) and before step (α-3), it may be passed as a step. (α-2 ') A step of curing the curable resin layer (Z2) to form a cured resin film.
In the step (α-2 '), when the curable resin layer (Z2) is hardened by heating, the temperature condition is preferably performed in a temperature environment that does not reach the expansion start temperature (t) of the thermally expandable particles.

<Step (α-3)>
Step (α-3) is performed by heating at a temperature above the thermal expansion start temperature (t) of the thermally expandable particles to separate the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II). , A step of obtaining a processing object with a resin film.
FIG. 4 (b) is a schematic cross-sectional view showing a state where separation occurs at the interface P by heat treatment.
FIG. 4 (b) shows a state where separation occurs in a state where the object to be processed and inspected is a sheet (II) for forming a resin film by the aforementioned heat treatment.

In the step (α-3), the "temperature above the expansion start temperature (t)" at the time of the heat treatment is preferably "the expansion start temperature (t) + 10 ° C" or more and the "expansion start temperature (t) + 60 ° C") Hereinafter, it is 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 during the heat treatment is provided on the support side. The interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) of the adhesive laminated body is easily separated.

In this manner, after the interface P is separated, the resin film-forming sheet (II) is adhered to the processing object with the resin film attached to the processing object.
In addition, when the curable resin layer (Z2) is not cured even after separation, the curable resin layer (Z2) is cured to form a cured resin film.
After the cured resin film is formed, the resin film-forming sheet (II) other than the curable resin layer (Z2) can be removed to obtain an object to be processed with a cured resin film.

[Manufacturing method of hardened package with hardened resin film]
By using the adhesive laminated body of the present invention, productivity is improved, and a hardened package with a hardened resin film can also be manufactured.
More specific examples of the method for producing a cured package with a cured resin film include a production method having the following steps (β-1) to (β-3).
Step (β-1): The surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate is adhered to the support, and at the same time, the semiconductor wafer is placed on the resin film-forming sheet (II). Step of hardening resin layer (Z2),
Step (β-2): a step of covering the semiconductor wafer with a sealing material, curing the sealing material, forming a hardened package in which the semiconductor wafer is encapsulated, and curing the hardening resin layer (Z2) to form a hardened resin film,
Step (β-3): separation occurs at the interface P between the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) by heating above the thermal expansion start temperature (t) of the thermally expandable particles. , A step of obtaining a hardened package with a hardened resin film.

<Step (β-1)>
Step (β-1) is to stick the surface of the adhesive layer (X1) of the adhesive sheet (I) of the aforementioned adhesive laminated body to the support, and at the same time, place the semiconductor wafer on the resin film forming sheet (II). Step of the curable resin layer (Z2).
The support system used in step (β-1) is as described above.
As the semiconductor wafer, a conventionally known one can be used, and the circuit surface is formed with an integrated circuit composed of circuit elements such as a transistor, a resistor, and a condenser.
In addition, it is preferable that the semiconductor wafer is placed on the surface of the curable resin layer (Z2) on the resin film forming sheet (II) to cover the back surface on the side opposite to the circuit surface. At this time, after mounting, the circuit of the semiconductor wafer is moved upward.
For the mounting of the semiconductor wafer, a known device such as a flip chip bonder or a die bonder can be used.
The array and number of semiconductor wafers to be arranged may be appropriately determined according to the purpose of the package form and the number of productions.

Here, such as FOWLP, FOPLP, etc., it is better to cover the semiconductor wafer with a packaging material in an area larger than the wafer size, not only the circuit surface of the semiconductor wafer, but also the surface area of the packaging material to form a rewiring layer.
Therefore, the semiconductor wafer is placed on a part of the surface of the hardening resin layer (Z2). A plurality of semiconductor wafers are arranged at a certain interval. It is preferable that the semiconductor wafers are placed on the surface. The plurality of semiconductor wafers CP are empty. It is more preferable that the matrix be arranged in a plurality of rows and a plurality of columns at a certain interval and placed on the surface.
The interval between the semiconductor wafers may be appropriately determined according to the shape of the intended package and the like.

<Step (β-2)>
The step (β-2) is formed by coating the semiconductor wafer with a packaging material (hereinafter also referred to as "covering treatment"), curing the packaging material (hereinafter also referred to as "hardening treatment"), and forming the semiconductor wafer into a package. A step of curing the package and curing the curable resin layer (Z2) to form a cured resin film.
The coating treatment in step (β-2) is performed by first covering at least the peripheral portion of the semiconductor wafer and the surface of the curable resin layer (Z2) with a sealing material. The packaging material covers the entire upward moving surface of the semiconductor wafer, and also fills the gaps between the plurality of semiconductor wafers.

The packaging material is to protect the semiconductor wafer and its accompanying components from external environmental influences.
The packaging material may be any suitable one as a semiconductor packaging material user, and examples thereof include a packaging material containing a thermosetting resin or a packaging material containing an energy ray-curable resin.
In addition, the packaging material may be solid, such as granules, flakes, or a liquid form in the form of a composition at room temperature. From the viewpoint of workability, a flake-shaped packaging material is preferred.

The method of using a packaging material to cover a semiconductor wafer and its peripheral portion can be appropriately selected and used according to the type of packaging material from the methods previously applicable to semiconductor packaging steps. For example, a roll lamination method, a vacuum pressing method, and a vacuum lamination method can be used. , Spin coating, die coating, transfer molding, compression molding, and the like.

In addition, after the coating process is performed, the packaging material is hardened to obtain a hardened package in which the semiconductor wafer is sealed with the hardened packaging material.
The coating treatment and hardening treatment in step (β-2) are preferably performed under a temperature condition that does not reach the expansion start temperature (t) of the thermally expandable particles.
The coating step and the hardening step may be performed separately. However, in the coating step, when the packaging material is heated, the packaging material may be directly hardened by the heating, or the coating step and the hardening step may be simultaneously performed.

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

<Step (β-3)>
Step (β-3) is separation at the interface P of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) by heating above the thermal expansion start temperature (t) of the thermally expandable particles. , A step of obtaining a hardened package with a hardened resin film.
By heating above the thermal expansion start temperature (t), the thermally expandable particles swell, and unevenness is generated on the surface of the adhesive sheet (I) on the substrate (Y2) side of the resin film forming sheet (II). As a result, the interface P can be easily separated at a time with only a slight force.
The temperature conditions of the aforementioned heat treatment in step (β-3) are as described above.

After the interface P is separated, a layer of the resin film-forming sheet (II) other than the curable resin layer (Z2) is removed to obtain a cured package with a cured resin film.
Then, steps such as grinding and hardening the package until the circuit surface of the semiconductor wafer is exposed, rewiring the circuit surface, or forming an external electrode pad, and connecting the external electrode pad to the external terminal electrode may be performed. In addition, after the hardened package is connected to the external terminal electrode, the semiconductor device can be manufactured by singulation.

[Example]

The present invention will be described more specifically based on the following examples, but the present invention is not limited to the following examples. In addition, the physical property values in the following manufacturing examples and examples are values measured by the following methods.

<Mass average molecular weight (Mw)>
A gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8020") was used, and the measurement was performed under the following conditions, and the value measured in terms of standard polystyrene conversion was used.

(Measurement conditions)
･ Column column: "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", and "TSK gel G1000HXL" (all manufactured by Tosoh Corporation) in order. ･ Column temperature: 40 ° C
･ Developing solvent: Tetrahydrofuran ･ Flow rate: 1.0mL / min

＜ Measurement of thickness of each layer ＞
Measured using a constant-pressure thickness measuring device (model: "PG-02J", standard specification: JIS K6783, Z1702, Z1709) manufactured by teclock Corporation.

<Average particle diameter (D ₅₀ ), 90% particle diameter (D ₉₀ ) of thermally expandable particles>
The particle distribution of the thermally expandable particles before expansion at 23 ° C. was measured using a laser diffraction type particle size distribution measurement device (for example, manufactured by Malvern, under the product name “Mastersizer 3000”).
It is then calculated from the particle size distribution of smaller particles corresponding to a cumulative volume frequency of 50% and a 90% particle diameter, and "heat-expandable particles were used as the 90 '(D ₅₀₎ mean particle diameter of the thermally expandable fine particles." % Particle size (D ₉₀ ) ".

<Storage elastic modulus E 'of the thermally expandable base material layer (Y1-1)>
The formed thermally expandable base material layer (Y1-1) was 5 mm in length × 30 mm in width × 200 μm in thickness, and the peeled material was removed as a test sample.
Using a dynamic viscoelasticity measuring device (manufactured by TA Instrument, product name "DMAQ800"), measurement was performed under conditions of a test start temperature of 0 ° C, a test end temperature of 300 ° C, a temperature increase rate of 3 ° C / min, a vibration number of 1Hz, and an amplitude of 20 μm. The storage elastic modulus E 'of the test sample at a predetermined temperature.

<Shear storage modulus G 'of the adhesive layers (X11) and (X12)>
The formed adhesive layer (X11) and (X12) were cut into a circle having a diameter of 8 mm, and a thickness of 3 mm after removing the release material was used as a test sample.
Using a viscoelasticity measuring device (manufactured by Anton Paar, device name "MCR300"), the test was performed by torsional shear under conditions of a test start temperature of 0 ° C, a test end temperature of 300 ° C, a temperature increase rate of 3 ° C / min, and a vibration frequency of 1Hz. Method to measure the shear storage modulus G 'of a test sample at a given temperature.

＜ Probe type initial viscosity ＞
The substrate to be measured was cut into a square of 10 mm on one side, and the test sample was left to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity).
Under the environment of 23 ° C and 50% RH (relative humidity), use a viscometer (manufactured by Japan Special Instrument Co., Ltd., product name "NTS-4800") to measure the surface of the test sample in accordance with JIS Z0237: 1991. Stick-type initial adhesion.
Specifically, a probe made of stainless steel having a diameter of 5 mm was brought into contact with the surface of the test sample at a contact load of 0.98 N / cm ² for 1 second, and then the probe was required to leave the surface of the test sample at a speed of 10 mm / second. The value obtained by the force is used as the probe-type initial viscosity of the test sample.

＜ Measurement of adhesive force of the 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 as an adhesive sheet with a substrate.
Then, remove the release film, and stick the adhesive surface of the upwardly moving adhesive layer to the stainless steel plate (SUS304 360 No. grinding), and leave it to stand for 24 hours under the environment of 23 ° C and 50% RH (relative humidity). Then, under the same environment, the adhesive force at 23 ° C. was measured by a 180 ° tensile peeling method in accordance with JIS Z0237: 2000 and a tensile speed of 300 mm / min.

<Measurement of Adhesiveness of Curable Resin Layer (Z2)>
Adhere the surface of the hardening resin layer (Z2) that moves upward to the stainless steel plate (SUS304 360 No. grinding) to be adhered, and leave it at 23 ° C and 50% RH (relative humidity) for 24 hours. Under the same environment, in accordance with JIS Z0237: 2000, the adhesive force at 23 ° C was measured by a 180 ° pull-peel method at a tensile speed of 300 mm / min.

Production Example 1 (Synthesis of Urethane Prepolymer)
In a reaction vessel under a nitrogen environment, with respect to 100 parts by mass (solid content ratio) of carbonate-type diol having a mass average molecular weight of 1,000, the equivalent of the hydroxyl group of the carbonate-type diol and the isocyanate group of isophorone diisocyanate Isophorone diisocyanate was prepared by setting the ratio to 1/1, and then 160 parts by mass of toluene was added, stirred under a nitrogen environment, and allowed to react at 80 ° C. for more than 6 hours until the isocyanate group concentration reached the theoretical amount.
Next, a solution of 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) diluted with 30 parts by mass of toluene was added, and the mixture was further reacted at 80 ° C for 6 hours until the isocyanate groups at both ends were eliminated. Thus, a urethane prepolymer having a mass average molecular weight of 29,000 was obtained.

Production Example 2 (synthesis of acrylic urethane resin)
In a reaction vessel under a nitrogen environment, 100 parts by mass of the urethane prepolymer (solid content ratio) and 117 parts by mass of the methmethacrylate (MMA) (solid content ratio) were added. , 5.1 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) (solid content ratio), 1.1 parts by mass of 1-thioglycerol (solid content ratio), and 50 parts by mass of toluene, and the temperature was raised while stirring To 105 ° C.
Then, in the reaction container, a solution obtained by diluting 2.2 parts by mass (solid content ratio) of a radical initiator (manufactured by Japan Finechem Co., Ltd., product name "ABN-E") with 210 parts by mass of toluene was maintained at 105 ° C. Dripped in 4 hours.
After completion of the dropping, the reaction was performed at 105 ° C. for 6 hours to obtain an acrylic urethane resin solution having a mass average molecular weight of 105,000.

Production Example 3 (Preparation of Curable Composition)
Each component of the following types and blending amounts (both "active ingredient ratio") was prepared, and then diluted with methyl ethyl ketone, and the solid content concentration (active ingredient concentration) of 61% by mass was uniformly stirred to prepare the hardenability. Composition solution.
･ Acrylic polymer: blending amount = 28 parts by mass
An acrylic polymer obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methacrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (Mass average molecular weight: 800,000, glass transition temperature: -1 ° C), which corresponds to the aforementioned component (A1).
･ Epoxy compound (1): formulated amount = 10.4 parts by mass of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828", epoxy equivalent weight = 184 to 194 g / eq), equivalent to the above components ( B11).
･ Epoxy compound (2): formulated amount = 5.2 parts by mass of dicyclopentadiene epoxy resin (manufactured by DIC Corporation, product name "EPICLONHP-7200HH", epoxy equivalent weight = 255 to 260 g / eq), equivalent to The component (B11).
･ Epoxy compound (3): blended amount = 1.7 parts by mass of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent = 800 to 900 g / eq), equivalent to the above components ( B11).
･ Thermal hardener: The blending amount = 0.42 parts by mass of dicyandiamide (manufactured by ADEKA Corporation, product name "ADK HARDENER EH-3636AS", active hydrogen content = 21g / eq), equivalent to the above-mentioned component (B12).
･ Hardening accelerator: formulated amount = 0.42 parts by mass
2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd. under the product name "CUREZOL 2PHZ") corresponds to the aforementioned component (B13).
･ Coloring agent: formulated amount = 0.20 parts by mass of carbon black (manufactured by Mitsubishi Chemical Corporation, product name "# MA650", average particle size = 28 nm), equivalent to the above-mentioned component (C).
･ Silane coupling agent: formulated amount = 0.09 parts by mass
3-Glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM403") corresponds to the aforementioned component (D).
･ Inorganic filler: Formulated amount = 55.5 parts by mass of silica filler (manufactured by admatechs, product name "SC2050MA", average particle size = 0.5 μm), equivalent to the above-mentioned component (E).

The details of the adhesive resin, additives, thermally expandable particles, release material, and adhesive resin used in the formation of each layer in the following examples are as follows.

＜ Adhesive resin ＞
･ Acrylic copolymer (i): It has a constituent unit derived from a raw material monomer formed from 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio) Mw 600,000 acrylic copolymer.
･ Acrylic copolymer (ii): It is derived from n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid = 86.0 / 8.0 / 5.0 /1.0 (mass ratio) The acrylic monomer copolymer of Mw 600,000 constituting unit of the raw material monomer.

＜ Additives ＞
･ Isocyanate crosslinking agent (i): manufactured by Tosoh Corporation, product name "coronateL", solid content concentration: 75% by mass.
･ Photopolymerization initiator (i): manufactured by BASF, product name "IRGACURE184", 1-hydroxy-cyclohexyl-phenyl-one.

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

＜ Peeling material ＞
･ Heavy release film: A release agent layer made of a silicone-based release agent is provided on one side of a polyethylene terephthalate (PET) film manufactured by Lintec Corporation under the product name "SP-PET382150". : 38 μm.
･ Light release film: A release agent layer made of a polysiloxane-based release agent is provided on one side of a PET film manufactured by Lintec Corporation under the product name "SP-PET381031". Thickness: 38 μm.

Example 1
As shown in the adhesive laminated body 2b shown in FIG. 2 (b), the second adhesive layer (X12) of the adhesive sheet (I) and the adhesive layer (X2) of the adhesive sheet (II) are produced in the following order: An adhesive laminated body having a structure in which a release material is re-laminated.

[1] Production of adhesive sheet (I)
(1-1) Formation of the first adhesive layer (X11) In an adhesive resin, that is, 100 parts by mass of the solid content of the acrylic copolymer (i), 5.0 parts by mass of the isocyanate-based crosslinking agent (i) is blended. (Solid content ratio), diluted with toluene and stirred uniformly to prepare an adhesive composition having a solid content concentration (effective component concentration) of 25% by mass.
Then, the surface of the release agent layer of the heavy release film was coated with the adhesive composition to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to form a first non-thermally expandable adhesive layer having a thickness of 5 μm. 1 Adhesive layer (X11).
The shear storage modulus G '(23) of the first adhesive layer (X11) at 23 ° C was 2.5 × 10 ⁵ Pa.
The adhesive force of the first adhesive layer (X11) measured according to the above method was 0.3 N / 25 mm.

(1-2) Formation of the second adhesive layer (X12) In an adhesive resin, that is, 100 parts by mass of the solid content of the acrylic copolymer (ii), 0.8 part by mass of the isocyanate-based crosslinking agent (i) is blended. (Solid content ratio), diluted with toluene and stirred uniformly to prepare an adhesive composition having a solid content concentration (effective component concentration) of 25% by mass.
Then, the surface of the release agent layer of the light release film was coated with the adhesive composition to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to form a second adhesive layer (X12) having a thickness of 10 μm. .
The shear storage modulus G '(23) of the second adhesive layer (X12) at 23 ° C was 9.0 × 10 ⁴ Pa.
The adhesive force of the second adhesive layer (X12) measured according to the above method was 1.0 N / 25 mm.

(1-3) Preparation of base material (Y1) In 100 parts by mass of the solid content of the acrylic urethane resin obtained in Production Example 2, 6.3 parts by mass of the isocyanate-based crosslinking agent (i) (solid (Component ratio), 1.4 parts by mass (solid content ratio) of dioctyltinbis (2-ethylhexanoate) as a catalyst, and the thermally expandable particles (i), diluted with toluene and stirred uniformly to prepare a solid component A resin composition having a concentration (active ingredient concentration) of 30% by mass.
The content of the thermally expandable particles (i) was 20% by mass based on the total amount (100% by mass) of the active ingredients in the obtained resin composition.
Then, a non-thermally expandable substrate, that is, a surface of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., with the product name "Cosmo Shine A4100", and a probe-type initial viscosity: 0mN / 5mmf) with a thickness of 50 µm Then, the resin composition was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to form a thermally expandable substrate layer (Y1-1) having a thickness of 50 μm.
Here, the PET film of the non-thermally expandable substrate corresponds to the non-thermally expandable substrate layer (Y1-2).

As a sample for measuring the physical properties of the thermally expandable base material layer (Y1-1),
The resin composition was coated on the surface of the release agent layer of the light release film to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to form a thermally expandable substrate layer (Y1-1) having a thickness of 50 μm. .
Then, according to the measurement method described above, the storage elastic modulus and the probe-type initial viscosity at each temperature of the thermally expandable substrate layer (Y1-1) were measured. The measurement results are as follows.
储存 Storage elastic modulus at 23 ° C E '(23) = 2.0 × 10 ⁸ Pa
储存 Storage elastic modulus at 100 ° C E '(100) = 3.0 × 10 ⁶ Pa
储存 Storage modulus of elasticity at 208 ° C E '(208) = 5.0 × 10 ⁵ Pa
･ Probe stick initial viscosity = 0mN / 5mmf

(1-4) Lamination of each layer The non-thermally expandable substrate layer (Y1-2) of the substrate (Y1) prepared in the above (1-3) and the second adhesive layer (X12) formed in the above (1-2) ), The heat-expandable base material layer (Y1-1) and the second adhesive layer (X12) formed by the above (1-2) were simultaneously bonded.
Then, a light release film / second adhesive layer (X12) / non-thermally expandable substrate layer (Y1-2) / thermally expandable substrate layer (Y1-1) / first adhesive layer (X11) / weight Adhesive sheet (I) obtained by sequentially stacking release films.

[2] Production of the resin film-forming sheet (II) The above-mentioned heavy release film was used as the substrate (Y2). A solution of the curable composition prepared in Production Example 3 was applied on the release-treated surface of the heavy release film to form a coating film. The coating film was dried at 120 ° C for 2 minutes to form a curable resin layer having a thickness of 25 μm. (Z2).
The adhesive force of the formed curable resin layer (Z2) was 0.5 N / 25 mm.
Then, the light-releasing film is formed on the surface area of the curable resin layer (Z2) to form a resin film-forming sheet which is laminated in the order of the substrate (Y2) / curable resin layer (Z2) / light-release film. (II).

[3] Production of Adhesive Laminated Body Remove the heavy release film of the adhesive sheet (I) produced in [1] above, and move the first adhesive layer (X11) and the resin film-forming sheet (II) upward. The surface of the heavy release film of the material (Y2) to which the release treatment was not applied was adhered to obtain an adhesive laminate.

For this adhesive laminate, the first adhesive layer (X11) on the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) before and after the heat treatment were measured according to the following method. The peeling force (F ₁ ), (F ₂ ) at the interface P in the case of separation occurs.
Results The peel force (F ₀ ) = 200mN / 25mm, the peel force (F ₁ ) = 0mN / 25 mm, and the ratio of the peel force (F ₁ ) to the peel force (F ₀ ) [(F ₁ ) / (F ₀ ) ] Is 0.

＜ Measurement of peeling force (F ₀ ) ＞
After the produced adhesive laminate is left at rest in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours, the heavy release film of the adhesive sheet (II) of the adhesive laminate is removed, and upwards The moving adhesive layer (X2) is adhered to the stainless steel plate (SUS304 360 No. grinding).
Next, the end portion of the stainless steel plate to which the adhesive laminate was adhered was fixed to a lower chuck of a universal tensile tester (manufactured by ORIENTEC Corporation, product name "TENSILON UTM-4-100").
In addition, the adhesive sheet (I) of the adhesive laminate is fixed by the upper suction cup of the universal tensile tester, so that the first adhesive layer (X11) and the adhesive sheet (II) of the adhesive laminate (I) are in the adhesive laminate. The interface P of the base material (Y2) is peeled.
Then, under the same environment as above, in accordance with JIS Z0237: 2000, by 180 ° pull-peel method, at a tensile speed of 300 mm / min, when peeling occurs at the interface P, the measured peel force is referred to as "peel force (F ₀ )"".

＜ Measurement of peeling force (F ₁ ) ＞
The heavy peeling film of the adhesive sheet (II) of the adhesive laminated body after the production is removed, and the upwardly moving adhesive layer (X2) is adhered to a stainless steel plate (SUS304 360).
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 substrate layer (Y1-2) of the adhesive laminate.
Then, similarly to the measurement of the peeling force (F ₀ ), under the above-mentioned conditions, an interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) is generated. The peeling force at the time of separation is referred to as "peeling force (F ₁ )".
When measuring the peeling force (F ₁ ), when the adhesive sheet (I) of the adhesive laminate is fixed by the suction cup on the upper part of the universal tensile testing machine, the adhesive sheet (I) is completely separated at the interface P, and when it cannot be fixed, At the end of the measurement, the peel force (F ₁ ) at this time was "0 mN / 25 mm".

Example 2
A cured package with a cured resin film was produced by the following procedure.

(1) Mounting of semiconductor wafer Remove the light release film on the adhesive sheet (I) side of the adhesive laminated body produced in Example 1, and move the second adhesive layer (X12) of the adhesive sheet (I) moving upward. ) The adhesive surface is adhered to the support (glass).
Then, the light release film on the resin film forming sheet (II) side was also removed. On the surface of the curable resin layer (Z2) of the resin film forming sheet (II) moved upward, 9 semiconductor wafers (each of which The wafer size is 6.4 mm × 6.4 mm, and the wafer thickness is 200 μm (# 2000). The back surface on the opposite side to the circuit surface of each semiconductor wafer is in contact with this surface, and it is placed with a necessary space therebetween.

(2) Formation of hardened package The surface of the nine semiconductor wafers and the hardenable resin layer (Z2) of at least the peripheral portion of the semiconductor wafer is covered with a sealing resin film, and a vacuum heating and pressure laminator (ROHM and "7024HP5" manufactured by HAAS Corporation) The encapsulating resin film is hardened to produce a hardened package.
The packaging conditions are as follows.
･ Pre-heating temperature: both workbench and partition are 100 ℃
･ Evacuation: 60 seconds ･ Dynamic pressing mode: 30 seconds ･ Static pressing mode: 10 seconds ･ Packing temperature: 180 ° C × 60 minutes The hardening resin layer (Z2) is also hardened under the above-mentioned environment to serve as a hardening resin film.

(3) After the separation of the interface P described in (2) above, the adhesive laminate is subjected to a heat treatment for 3 minutes at 240 ° C which is the expansion start temperature (208 ° C) of the thermally expandable particles. The interface P between the adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film-forming sheet (II) can be easily separated at one time.
Then, after the separation, the base material (Y2) of the resin film-forming sheet (II) was also removed to obtain a cured package with a cured resin film.

1a, 1b, 1c, 1d, 2‧‧‧ Adhesive laminates

(I) ‧‧‧Adhesive sheet

(X1) ‧‧‧Adhesive layer

(X11) ‧‧‧The first adhesive layer

(X12) ‧‧‧Second Adhesive Layer

(Y1) ‧‧‧Substrate

(Y1-1) ‧‧‧Thermally expandable base material layer

(Y1-2) ‧‧‧Non-thermally expandable substrate layer

(II) ‧‧‧ Sheet for resin film formation

(Y2) ‧‧‧Substrate

(Z2) ‧‧‧curable resin layer

50‧‧‧ support

60‧‧‧Processing object

P‧‧‧ interface

[Fig. 1] A schematic cross-sectional view of the adhesive laminated body showing the constitution of the adhesive laminated body in the first aspect of the present invention.

[Fig. 2] A schematic cross-sectional view of the adhesive laminated body showing the constitution of the adhesive laminated body in the second aspect of the present invention.

[Fig. 3] A schematic cross-sectional view of the adhesive laminated body showing the constitution of the adhesive laminated body in a third aspect of the present invention.

[Fig. 4] (a) is a schematic cross-sectional view showing an example of a state where a processing inspection object is fixed to a support through the adhesive laminated body of the present invention, and (b) is a view showing separation at the interface P by heat treatment A schematic sectional view of the state.

Claims (13)

An adhesive laminate comprising a substrate (Y1) and an adhesive layer (X1), one of which includes a thermally expandable adhesive sheet (I) having thermally expandable particles, A sheet (II) for forming a resin film having a base material (Y2) and a curable resin layer (Z2), The adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated, Adhesive laminated body for fixing a processing object to a support body when performing specific processing, The surface of the adhesive layer (X1) of the adhesive sheet (I) is a surface which is adhered 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 adhered, By heat treatment at a temperature equal to or higher than the thermal expansion start temperature (t) of the thermally expandable particles, the interface (P) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) can be separated. . For example, the adhesive laminated body of claim 1, wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270 ° C. The adhesive laminated body according to claim 1 or 2, wherein the substrate (Y1) included in the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing the aforementioned thermally expandable particles. For example, the adhesive laminate of claim 3, wherein the substrate (Y1) of the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). For example, the adhesive laminate of claim 3 or 4, wherein the thermally expandable substrate layer (Y1-1) of the substrate (Y1) of the adhesive sheet (I) and the substrate (II) of the resin film-forming sheet (II) are adhered ( Y2) is directly laminated. For example, the adhesive laminate according to any one of claims 3 to 5, wherein the adhesive sheet (I) has a first adhesive layer (X11) and a second adhesive layer (X12), and the substrate (Y1) is held. Composition of The first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated, The surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface adhered to the support. For example, the adhesive laminate of claim 1 or 2, wherein the adhesive sheet (I) has a structure in which the substrate (Y1) is held by the first adhesive layer (X11) and the second adhesive layer (X12), The first adhesive layer (X11) is a thermally expandable adhesive layer containing the aforementioned thermally expandable particles, The second adhesive layer (X12) is a non-thermally expandable adhesive layer, The first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) are directly laminated, The surface of the second adhesive layer (X12) of the adhesive sheet (I) is a surface adhered to the support. The adhesive laminated body according to any one of claims 1 to 7, wherein the surface of the substrate (Y2) laminated with the adhesive sheet (I) is a surface to which a peeling treatment has been applied. The adhesive laminate according to any one of claims 1 to 8, wherein the curable resin layer (Z2) is formed of a curable composition (z) containing a polymer component (A) and a curable component (B). Layers. A method for manufacturing a processing object with a resin film, which is a method for manufacturing a processing object with a resin film by using the adhesive laminate according to any one of claims 1 to 9, It has the following steps (α-1) ~ (α-3): Step (α-1): The surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate is adhered to the support, and at the same time, the curable resin layer (II) of the resin film forming sheet (II) ( Z2) The step of placing or adhering the processing object on the surface, Step (α-2): a step of performing a specific processing on the aforementioned processing object, Step (α-3): The interface (P) at the interface (Y) between the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) is heated by the thermal expansion starting temperature (t) or more of the thermally expandable particles. A step of separating and obtaining a processing object with a resin film. For example, in the method for manufacturing a processing object with a resin film according to claim 10, in the step (α-2), the curable resin layer (Z2) is cured to form a cured resin film. For example, the method for manufacturing a processing object with a resin film according to claim 10, wherein after the step (α-2) and before the step (α-3), the method has the following step (α-2 '), Step (α-2 '): A step of curing the curable resin layer (Z2) to form a cured resin film. A method for manufacturing a hardened package with a hardened resin film, which is a method for manufacturing a hardened package with a hardened resin film by using the adhesive laminated body according to any one of claims 1 to 9, It has the following steps (β-1) ~ (β-3): Step (β-1): The surface of the adhesive layer (X1) of the adhesive sheet (I) of the above-mentioned adhesive laminate is adhered to the support, and at the same time, the semiconductor wafer is placed on the resin film-forming sheet (II). Step of hardening resin layer (Z2), Step (β-2): a step of covering the semiconductor wafer with a sealing material, curing the sealing material, forming a hardened package in which the semiconductor wafer is encapsulated, and curing the hardening resin layer (Z2) to form a hardened resin film, Step (β-3): The interface (P) between the adhesive sheet (I) and the substrate (Y2) of the resin film forming sheet (II) is heated by the thermal expansion starting temperature (t) or more of the thermally expandable particles. A step of generating separation to obtain a cured package with a cured resin film.