JPWO2019181447A1 - Manufacturing method of processed products and adhesive laminate - Google Patents

Abstract

A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and an adhesive layer (X1) and containing heat-expandable particles in any of the layers, and a base material (Y2) and a pressure-sensitive adhesive layer (X2). ) Is provided, and a processed product is manufactured using an adhesive laminate in which the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) are directly laminated. The step of attaching the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and attaching the object to be processed to the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate (1). Step of performing one or more processing on the object to be processed (2) By heating the thermally expandable particles at a temperature equal to or higher than the thermal expansion start temperature, the object to be processed is placed on the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate. The process (3) of separating the adhesive laminate at the interface between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) while maintaining the attached state is further included. The step (4) of performing at least one of cutting and grinding on the surface opposite to the surface to which the adhesive layer (X2) of the object is attached is performed in step (2) or after step (3). A method for manufacturing a processed product, which is carried out in.

Description

The present invention relates to a method for manufacturing a processed product that has been subjected to at least one of cutting and grinding, and an adhesive laminate used in the manufacturing method.

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

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

Japanese Patent No. 3594853

In the process of processing using the adhesive sheet described in Patent Document 1, the object to be processed using the adhesive sheet (hereinafter, also referred to as “processed object”) is temporarily fixed, and the object to be processed is subjected to predetermined processing. After being applied, the object to be processed is separated from the adhesive sheet.
By the way, particularly in the production of electronic parts and the like, a plurality of processing steps including at least one of a step of cutting an object to be machined and a step of grinding are often performed.
Therefore, for example, after at least one of the processing steps of cutting and grinding the processing object is performed on the processing object temporarily fixed to the adhesive sheet, the processing object is removed from the adhesive sheet. The separated object to be processed may be attached to a new adhesive sheet and used in the next step.
Further, after a processing process other than the step of cutting the object to be processed and the process of grinding is performed on the object to be processed temporarily fixed to the adhesive sheet, the object to be processed is separated from the adhesive sheet and separated. The object to be processed may be attached to a new adhesive sheet, and at least one of the steps of cutting and grinding the object to be processed may be performed.

However, if the product is manufactured by the above procedure, not only the work becomes complicated but also the productivity of the product is lowered. Therefore, it is desired to establish a method capable of improving the productivity of the product while suppressing the complexity of the work.

According to the present invention, after the object to be processed is fixed to the support and the object to be processed is processed, the object to be processed can be easily separated from the support collectively with a slight force. The object to be processed separated from the support can be subjected to the processing of the next step in a state of being attached to the adhesive sheet, and the object to be processed can be processed at least at any timing before and after the object to be processed is separated from the support. A method for manufacturing a processed product that has been subjected to at least one of cutting and grinding, and at least one of cutting and grinding, which can perform at least one of cutting and grinding. It is an object of the present invention to provide an adhesive laminate for manufacturing a processed product.

The present inventors have a heat-expandable pressure-sensitive adhesive sheet (I) having a base material and a pressure-sensitive adhesive layer, and including a layer containing heat-expandable particles in any of the layers, and a base material and a pressure-sensitive adhesive layer. Using an adhesive laminate comprising the adhesive sheet (II) and in which the adhesive sheet (I) and the base material of the adhesive sheet (II) are directly laminated, at least one of cutting and grinding is performed. It has been found that the above-mentioned problems can be solved by manufacturing the processed products.

That is, the present invention relates to the following [1] to [17].
[1] A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1) and containing heat-expandable particles having a thermal expansion start temperature (t) in any of the layers, and An adhesive laminate comprising a pressure-sensitive adhesive sheet (II) having a base material (Y2) and an adhesive layer (X2), and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. Is a method of manufacturing a processed product that has been subjected to at least one of cutting and grinding.
The following steps (1) to (3) are performed in this order.
Step (1): A step of attaching the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and attaching the object to be processed to the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate. -Step (2): A step of performing one or more processing on the processing object-Step (3): By heating the heat-expandable particles at a thermal expansion start temperature (t) or higher, the processing object is adhered to the adhesive. The adhesive laminate is separated at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) while maintaining the state of being attached to the surface of the adhesive layer (X2) of the adhesive laminate. Steps to be performed Further, it has the following step (4).
Step (4): A step of performing at least one of cutting and grinding on the surface of the object to be processed opposite to the surface to which the adhesive layer (X2) is attached. The step (4) is as follows. A method for producing a processed product, which is carried out in at least one of (X) and (Y).
(X): Performed in the step (2) as the one or more processes (Y): Performed after the step (3) [2] Thermal expansion start temperature (t) of the thermally expandable particles The production method according to the above [1], wherein the temperature is 60 to 270 ° C.
[3] The production according to the above [1] or [2], wherein the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) containing the heat-expandable particles. Method.
[4] In the above [3], the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2). The manufacturing method described.
[5] The above-mentioned [5], wherein the heat-expandable base material layer (Y1-1) of the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. 3] or the manufacturing method according to [4].
[6] The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12), and the first pressure-sensitive adhesive sheet (I). The pressure-sensitive adhesive layer (X11) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated, and the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is the support. The manufacturing method according to the above [3] to [5], which is a surface to be attached to the above.
[7] The first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles.
The second pressure-sensitive adhesive layer (X12) is a non-thermally expandable pressure-sensitive adhesive layer, and the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly connected to each other. The production method according to the above [1] or [2], wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) having a laminated structure is a surface to be attached to the support.
[8] The production method according to the above [6] or [7], wherein the surface on the side where the first pressure-sensitive adhesive layer (X11) of the base material (Y1) is laminated is the surface to which the easy-adhesion treatment is applied.
[9] The production method according to the above [1] to [8], wherein the surface on the side where the adhesive sheet (I) of the base material (Y2) is laminated is the surface to which the peeling treatment has been performed.
[10] The production method according to the above [1] to [9], wherein the pressure-sensitive adhesive sheet (II) has an intermediate layer (Z2) between the base material (Y2) and the pressure-sensitive adhesive layer (X2).
[11] The production method according to the above [1] to [10], wherein the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is an energy ray-curable pressure-sensitive adhesive layer.
[12] The production method according to the above [1] to [11], wherein the adhesive sheet (II) satisfies one or more of the following requirements (α) to (γ).
-Requirement (α): Young's modulus of the base material (Y2) is 1.0 MPa or more.
-Requirement (β): The thickness of the base material (Y2) is 5 μm or more.
-Requirement (γ): The storage elastic modulus G'(23 ° C.) of the pressure-sensitive adhesive layer (X2) is 0.1 MPa or more.
[13] The object to be processed is a semiconductor wafer.
The one or more processes in the step (2) include the following steps (2-A).
Step (2-A): A step of forming a modified region serving as a division starting point on the semiconductor wafer. The step (4) is the following step (4-A).
Step (4-A): A step of grinding the surface of the semiconductor wafer opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached. ) Or (YA), the production method according to the above [1] to [12].
(XA): Performed after the step (2-A) as the one or more processes (YA): Performed after the step (3) [14] The processed object is a semiconductor chip. And
The one or more processes in the step (2) include the following steps (2-B).
Step (2-B): The semiconductor chip and the peripheral portion of the adhesive surface of the pressure-sensitive adhesive layer (X2) are covered with a sealing material, and the sealing material is cured. Step of obtaining a cured encapsulant obtained by encapsulating the semiconductor chip in a cured encapsulant The step (4) is carried out in at least one of the following (XB) and (YB). The production method according to [1] to [12].
(X-B): Performed after the step (2-B) as the one or more processes (Y-B): Performed after the step (3) [15] The processed object is a division starting point. It is a semiconductor wafer having a modified region that becomes
The production method according to the above [1] to [12], wherein the step (4) is the following step (4-A).
Step (4-A): A step of grinding the surface of the semiconductor wafer opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached [16] A notch groove in which the object to be processed is a division starting point. Is a semiconductor wafer with
The production method according to the above [1] to [12], wherein the step (1) is the following step (1-C), and the step (4) is the following step (4-C).
Step (1-C): The surface of the adhesive layer (X1) of the adhesive laminate is attached to the support, and the semiconductor wafer is cut into the surface of the adhesive layer (X2) of the adhesive laminate. Step / Step (4-C) of attaching the grooved surface: A step of grinding the surface of the semiconductor wafer opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached [17] Substrate ( It has Y1) and an adhesive layer (X1), and has a heat-expandable pressure-sensitive adhesive sheet (I) containing heat-expandable particles in any of the layers, and a base material (Y2) and a pressure-sensitive adhesive layer (X2). Manufactures a processed product having an adhesive sheet (II) and having at least one of cutting and grinding processed, in which the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) are directly laminated. Adhesive laminate for use.

According to the present invention, after the object to be processed is fixed to the support and the object to be processed is processed, the object to be processed can be easily separated from the support collectively with a slight force. Moreover, the object to be processed separated from the support can be subjected to the processing of the next step in a state of being attached to the adhesive sheet, and the processing can be performed at least at any timing before and after the object to be processed is separated from the support. A method for manufacturing a processed product that has been subjected to at least one of cutting and grinding, and at least one of cutting and grinding, which can perform at least one of cutting and grinding of an object. It is possible to provide an adhesive laminate for manufacturing the processed product.

It is sectional drawing of the sticky laminate which shows the structure of the sticky laminate of the 1st aspect used in the manufacturing method of this invention. It is sectional drawing of the adhesive laminate which shows the structure of the adhesive laminate of the 2nd aspect used in the manufacturing method of this invention. It is sectional drawing of the adhesive laminate which shows the structure of the adhesive laminate of the 3rd aspect used in the manufacturing method of this invention. It is the schematic which shows an example of the manufacturing method of this invention. It is the schematic which shows another example of the manufacturing method of this invention.

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

As used herein, the term "active ingredient" refers to a component contained in a target composition excluding a diluting solvent.
In the present specification, the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically, a value measured based on the method described in Examples. Is.
In the present specification, for example, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also used.
In the present specification, the lower limit value and the upper limit value described stepwise for a preferable numerical range (for example, a range such as content) can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". You can also do it.

[Manufacturing method of processed products]
The method for producing a processed product of the present invention has a base material (Y1) and an adhesive layer (X1), and one of the layers contains thermally expandable particles having a thermal expansion start temperature (t). The sheet (I) and the pressure-sensitive adhesive sheet (II) having the base material (Y2) and the pressure-sensitive adhesive layer (X2) are provided, and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. It is a method of manufacturing a processed product which has been subjected to at least one of cutting and grinding using the adhesive laminate.
The following steps (1) to (3) are performed in this order.
Step (1): A step of attaching the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and attaching the object to be processed to the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate. -Step (2): A step of performing one or more processing on the processing object-Step (3): By heating the heat-expandable particles at a thermal expansion start temperature (t) or higher, the processing object is adhered to the adhesive. The adhesive laminate is separated at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) while maintaining the state of being attached to the surface of the adhesive layer (X2) of the adhesive laminate. Steps to be performed Further, it has the following step (4).
Step (4): A step of performing at least one of cutting and grinding on the surface of the object to be processed opposite to the surface to which the adhesive layer (X2) is attached. The step (4) is as follows. It is carried out in at least one of (X) and (Y).
(X): Performed in the step (2) as the one or more processes (Y): Performed after the step (3) Hereinafter, the adhesive laminate used in the production method of the present invention will be described. After that, each manufacturing process including the steps (1) to (4) will be described.

[Structure of adhesive laminate]
The pressure-sensitive adhesive laminate used in the production method of the present invention has a base material (Y1) and a pressure-sensitive adhesive layer (X1), and the heat-expandable pressure-sensitive adhesive sheet (I) contains heat-expandable particles in any of the layers. And the pressure-sensitive adhesive sheet (II) having the base material (Y2) and the pressure-sensitive adhesive layer (X2), and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. Therefore, it is used to fix the object to be processed to the support when performing a predetermined process on the object to be processed.
In the present specification, the predetermined processing means the processing of the step (2) in the manufacturing method of the present invention. In the present invention, the step (4) may be carried out as one or more of the processes in the step (2). Therefore, the predetermined processing may also include the step (4) in the manufacturing method of the present invention.
In the adhesive laminate used in the production method of the present invention, the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is the surface to which the support is attached. When the pressure-sensitive adhesive sheet (I) has a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), the surface of the second pressure-sensitive adhesive layer (X12) is the surface to which the support is attached, and the first pressure-sensitive adhesive layer (X12) is attached. The surface of the agent layer (X11) is a surface to be laminated on the base material (Y2) side of the pressure-sensitive adhesive sheet (II). The surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is the surface on which the object to be processed is attached.
The adhesive laminate used in the production method of the present invention is subjected to heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles, whereby the adhesive sheet (I) and the base material of the adhesive sheet (II) are used. It can be separated at the interface P with (Y2). In the following description, the heat treatment is also referred to as "heat treatment for separation".
1 to 3 are schematic cross-sectional views showing the configurations of the adhesive laminates of the first aspect, the second aspect, and the third aspect used in the production method of the present invention, respectively.

<Adhesive laminate of the first aspect>
Examples of the adhesive laminate of the first aspect used in the production method of the present invention include the adhesive laminates 1a and 1b shown in FIGS. 1A and 1B.
The adhesive laminates 1a and 1b include a pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1), and a pressure-sensitive adhesive sheet (II) having a base material (Y2) and a pressure-sensitive adhesive layer (X2). The base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.

In the adhesive laminate used in the production method of the present invention, any layer of the adhesive sheet (I) is a layer containing thermal expansion particles so that the adhesive laminate can be separated at the interface P by heat treatment for separation. ..
In the adhesive laminate used in the production method of the present invention, the heat-expandable particles expand by the heat treatment for separation, and the surface of the layer containing the heat-expandable particles becomes uneven. As a result, the contact area between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) is reduced.
As a result, the object to be processed is attached on the surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II), and after performing the predetermined processing, the base material (Y2) of the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive sheet (II) is applied. ), It is possible to obtain a processed object in a state of being attached to the adhesive sheet (II) which has been subjected to a predetermined process.

Therefore, according to the manufacturing method of the present invention, the object to be processed can be fixed to the support via the above-mentioned adhesive laminate to carry out a predetermined process, and the object to be processed has been subjected to the predetermined process. Objects can be easily separated from the support all at once with a small amount of force. Moreover, the processed object separated from the support can be used as it is in the next step in a state of being attached to the adhesive sheet (II).
Therefore, it is not necessary to attach the separated processed object that has been subjected to a predetermined process to a new adhesive sheet, and the workability and the productivity of the product can be improved.

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

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

Further, in the adhesive laminate 1b shown in FIG. 1B, the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded by the heat treatment for separation. However, the surface of the base material (Y1) on the pressure-sensitive adhesive sheet (II) side is uneven, and the contact area between the base material (Y1) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) is reduced.
On the other hand, since the non-thermally expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion due to heat treatment, the surface of the base material (Y1) on the pressure-sensitive adhesive layer (X1) side. It is difficult for unevenness to be formed on the surface. As a result, unevenness can be efficiently formed on the surface of the base material (Y1) on the pressure-sensitive adhesive sheet (II) side.
As a result, the adhesive laminate 1b can be easily separated at the interface P between the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) at once with a slight force. It becomes.
As in the case of the adhesive laminate 1a, the interface P is formed by forming the adhesive layer (X1) of the adhesive laminate 1b from an adhesive composition having a high adhesive force to the support. It is also possible to design it so that it can be separated more easily.

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

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

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

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

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

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

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

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

In the adhesive laminate 2 shown in FIG. 3, the heat treatment for separation causes irregularities on the surface of the heat-expandable pressure-sensitive adhesive layer, which is the first pressure-sensitive adhesive layer (X11). The contact area of the pressure-sensitive adhesive sheet (II) with the base material (Y2) is reduced.
On the other hand, since the base material (Y1), which is a non-thermally expandable base material, is laminated on the surface of the first pressure-sensitive adhesive layer (X11) on the base material (Y1) side, unevenness is unlikely to occur. Therefore, irregularities are efficiently formed on the surface of the first pressure-sensitive adhesive layer (X11) on the pressure-sensitive adhesive sheet (II) side.
As a result, the adhesive laminate 2 can be easily put together at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) with a slight force. Can be separated into.

<Structure of adhesive laminate with release material>
In one aspect of the adhesive laminate used in the production method of the present invention, one or both of the surface of the pressure-sensitive adhesive layer (X1) to which the support is attached and the surface of the pressure-sensitive adhesive layer (X2) to which the object to be processed is attached. , Further, a release material may be laminated.
Further, for example, in the adhesive laminates 1a and 1b shown in FIGS. 1A and 1B, the adhesive surfaces of one of the adhesive layer (X1) and the adhesive layer (X2) are peeled off on both sides. A roll-shaped structure may be obtained in which the release material is laminated. The adhesive laminates 1c and 1d shown in FIGS. 2 (a) and 2 (b) and the adhesive laminate 2 shown in FIG. 3 may also be wound in a roll shape in the same manner.

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

Further, before the heat treatment, from the viewpoint of sufficiently fixing the object to be processed so as not to adversely affect the processing work, the layer between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II). High adhesion is preferable.
From the above viewpoint, in the adhesive laminate of one aspect used in the production method of the present invention, the peeling force (F ₀ ) at the time of separation at the interface P before the heat treatment is preferably 100 mN / 25 mm or more. It is more preferably 300 mN / 25 mm or more, further preferably 500 mN / 25 mm or more, and preferably 50,000 mN / 25 mm or less.

In one aspect of the adhesive laminate used in the production method of the present invention, the peeling force (F ₀ ) is larger than the peeling force (F _1). Specifically, the ratio [(F ₁ ) / (F 0)] of the peeling force (F ₁ ) to the peeling force (F _{0 ) is preferably 0 to} 0.9, more preferably 0 to 0.8. , More preferably 0 to 0.5, and even more preferably 0 to 0.2.

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

In one aspect of the adhesive laminate used in the production method of the present invention, the pressure-sensitive adhesive layer (X1) (first pressure-sensitive adhesive layer (X11) and second pressure-sensitive adhesive) of the pressure-sensitive adhesive sheet (I) at room temperature (23 ° C.). The adhesive strength of the layer (X12)) and the adhesive strength of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) are independently, preferably 0.1 to 10.0 N / 25 mm, more preferably 0. It is .2 to 8.0 N / 25 mm, more preferably 0.4 to 6.0 N / 25 mm, and even more preferably 0.5 to 4.0 N / 25 mm.
When the pressure-sensitive adhesive sheet (I) has a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), the adhesive strengths of the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are different, respectively. The above range is preferable, but from the viewpoint of improving the adhesion to the support and making it easier to separate all at once at the interface P, the second pressure-sensitive adhesive layer (X12) to be attached to the support It is more preferable that the adhesive strength is higher than the adhesive strength of the first pressure-sensitive adhesive layer (X11).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Thermal expandable particles>
The thermally expandable particles used in the present invention may be particles that expand by heating, but are preferably particles whose expansion start temperature (t) is adjusted to 60 to 270 ° C. The expansion start temperature (t) is appropriately selected depending on the use of the adhesive laminate.
For example, in the manufacturing method of the present invention, when the adhesive laminate is not exposed to a high temperature environment in steps (1) and (2) (for example, a modified region as a division starting point is formed inside the semiconductor wafer). It is preferable that the expansion start temperature of the thermally expandable particles is as low as possible within the above temperature range. As a result, the heating energy required to separate the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive sheet (1I) can be reduced, and the manufacturing cost of the cut product and / or the ground product can be reduced. Further, the adhesive sheet (I) and the adhesive sheet (1I) can be separated without giving an excessive heat history to the object to be processed.
In the present specification, the expansion start temperature (t) of the heat-expandable particles means a value measured based on the following method.

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

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

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

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

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

The maximum volume expansion rate when the thermally expandable particles used in one embodiment of the present invention are heated to a temperature equal to or higher than the expansion start temperature (t) is preferably 1.5 to 100 times, more preferably 2 to 80 times, and further. It is preferably 2.5 to 60 times, and even more preferably 3 to 40 times.

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

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

Storage modulus E defined in requirement (1) of the heat-expandable base layer (Y1-1) used in the present invention '(t), from the above viewpoint, preferably not more than 9.0 × ¹⁰ 6 Pa, more preferably Is 8.0 × 10 ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.
In addition, the flow of expanded heat-expandable particles is suppressed, and the shape-retainability of the unevenness formed on the surface of the adhesive sheet (I) on the side where the adhesive sheet (II) is laminated with the base material (Y2) is improved. The storage elastic modulus E'(t) specified in the requirement (1) of the heat-expandable base material layer (Y1-1) is preferably set from the viewpoint of allowing the particles to be separated more easily at the interface P with a slight force. It is 1.0 × 10 ³ Pa or more, more preferably 1.0 × 10 ⁴ Pa or more, and further preferably 1.0 × 10 ⁵ Pa or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the polyisocyanate used as a raw material for the urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
These polyvalent isocyanates may be used alone or in combination of two or more.
Further, these polyvalent isocyanates may be a trimethylolpropan adduct-type modified product, a Biuret-type modified product reacted with water, or an isocyanurate-type modified product containing an isocyanurate ring.

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

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

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

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

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

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

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

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

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

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

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

The acrylic urethane resin (U1) used in one embodiment of the present invention is obtained by mixing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester and polymerizing both.
In the polymerization, it is preferable to further add a radical initiator.

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

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

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

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

For example, the acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin is a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof with the above-mentioned non-modified olefin-based resin. Can be mentioned.
Examples of the unsaturated carboxylic acid or its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, and itaconic anhydride. , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornendicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like.
The unsaturated carboxylic acid or its anhydride may be used alone or in combination of two or more.

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

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

(Resin other than acrylic urethane resin and olefin resin)
In one aspect of the present invention, the resin composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylic nitrile-butadiene-styrene co-weight. Combined; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resin; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; Fluorescent resin and the like can be mentioned.

However, from the viewpoint of forming the heat-expandable base material layer (Y1-1) satisfying the above requirement (1), the content ratio of the acrylic urethane resin and the resin other than the olefin resin in the resin composition (y) is determined. Less is preferable.
The content ratio of the resin other than the acrylic urethane resin and the olefin resin is preferably less than 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). Less than, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, still more preferably less than 1 part by mass.

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

The types and shapes of the heat-expandable particles to be blended in the solvent-free resin composition (y1) and the blending amount (content) are as described above.

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

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

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

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

The content ratio [oligomer / energy ray-polymerizable monomer] of the oligomer to the energy ray-polymerizable monomer in the solvent-free resin composition (y1) is preferably 20/80 to 90 / by mass ratio. 10, more preferably 30/70 to 85/15, still more preferably 35/65 to 80/20.

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

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

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

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

Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfate paper, glassin paper and the like.
Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyethylene terephthalate and poly. Polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; Polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; fluorine resin and the like can be mentioned.
Examples of the metal include aluminum, tin, chromium, titanium and the like.

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

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

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

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

Further, the non-thermally expandable base material layer (Y1-2) may contain thermally expandable particles as long as the volume change rate is within the above range. For example, by selecting the resin contained in the non-thermally expandable base material layer (Y1-2), it is possible to adjust the volume change rate within the above range even if the thermally expandable particles are contained. ..
However, the smaller the content of the heat-expandable particles in the non-heat-expandable base material layer (Y1-2), the more preferable.
The specific content of the heat-expandable particles is usually less than 3% by mass, preferably less than 1% by mass, based on the total mass (100% by mass) of the non-heat-expandable base material layer (Y1-2). It is more preferably less than 0.1% by mass, further preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass. More preferably, the non-thermally expandable base material layer (Y1-2) does not contain the thermally expandable particles.

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

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

Specific examples of the adhesive resin include rubber resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins.
These adhesive resins may be used alone or in combination of two or more.
When these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and block copolymers, random copolymers, and graft copolymers are used. It may be any of the polymers.

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

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

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

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

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

The acrylic resin used in one embodiment of the present invention includes a structural unit (a1) derived from an alkyl (meth) acrylate (a1') (hereinafter, also referred to as "monomer (a1')") and a functional group-containing monomer (a2). An acrylic copolymer (A1) having a structural unit (a2) derived from') (hereinafter, also referred to as "monomer (a2')") is more preferable.

The number of carbon atoms of the alkyl group contained in the monomer (a1') is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and even more preferably 4 to 8 from the viewpoint of improving the adhesive properties. Is.
The alkyl group contained in the monomer (a1') may be a straight chain alkyl group or a branched chain alkyl group.

Examples of the monomer (a1') include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (). Examples thereof include meta) acrylate and stearyl (meth) acrylate.
These monomers (a1') may be used alone or in combination of two or more.
As the monomer (a1'), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.

The content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, even more preferably 80 to 95.0% by mass.

Examples of the functional group contained in the monomer (a2') include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like.
That is, examples of the monomer (a2') include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
These monomers (a2') may be used alone or in combination of two or more.
Among these, as the monomer (a2'), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.

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

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

The content of the structural unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 1.0 to 30% by mass, and even more preferably 3.0 to 25% by mass.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').
In the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1). ~ 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.

Examples of the monomer (a3') include olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylates, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate. (Meta) Acrylate; Examples thereof include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholine, and N-vinylpyrrolidone.

Further, the acrylic copolymer (A1) may be an energy ray-curable acrylic copolymer in which a polymerizable functional group is introduced into the main chain and / or the side chain.
The polymerizable functional group and the energy ray are as described above.
The polymerizable functional group is a substituent capable of binding to the acrylic copolymer having the above-mentioned structural units (a1) and (a2) and the functional group having the structural unit (a2) of the acrylic copolymer. It can be introduced by reacting with a polymerizable compound (Xa) having a polymerizable functional group.
Examples of the polymerizable compound (Xa) include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, and (meth). Acrylic acid and the like can be mentioned.

(Crosslinking agent)
In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains a pressure-sensitive adhesive resin having a functional group like the above-mentioned acrylic copolymer (A1), it may further contain a cross-linking agent. preferable.
The cross-linking agent reacts with a tacky resin having a functional group and cross-links the tacky resins with the functional group as a cross-linking starting point.

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

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

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

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

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

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

(Photopolymerization initiator)
In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains an energy ray-curable pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin, it is preferable that the pressure-sensitive adhesive composition (x1) further contains a photopolymerization initiator.
By preparing a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive resin and a photopolymerization initiator, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be subjected to irradiation with relatively low-energy energy rays. , The curing reaction can be sufficiently advanced, and the adhesive strength can be adjusted to a desired range.
Examples of the photopolymerization initiator used in one embodiment of the present invention include the same photopolymerization initiators used in the above-mentioned solvent-free 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 further preferably 0. It is 05 to 2 parts by mass.

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

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

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

On the other hand, when the pressure-sensitive adhesive layer (X1) is a non-heat-expandable pressure-sensitive adhesive layer, the content of the heat-expandable particles in the non-heat-expandable pressure-sensitive adhesive composition which is a material for forming the non-heat-expandable pressure-sensitive adhesive layer is It is preferable that the amount is as small as possible.
The content of the heat-expandable particles is preferably relative to the total amount (100% by mass) of the active ingredient of the non-heat-expandable pressure-sensitive adhesive composition or the total mass (100% by mass) of the non-heat-expandable pressure-sensitive adhesive layer. It is less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass. More preferably, the non-thermally expandable pressure-sensitive adhesive composition or the non-heat-expandable pressure-sensitive adhesive layer does not contain the heat-expandable particles.

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

In the present specification, the storage shear elastic modulus G'(23) of the pressure-sensitive adhesive layer means a value measured by the method described in the examples.

[Structure of adhesive sheet (II)]
The pressure-sensitive adhesive sheet (II) contained in the pressure-sensitive adhesive laminate used in the production method of the present invention has a base material (Y2) and a pressure-sensitive adhesive layer (X2), and the base material (Y2) is directly laminated with the pressure-sensitive adhesive sheet (I). To do.
From the viewpoint of improving the interlayer adhesion between the base material (Y2) and the pressure-sensitive adhesive layer (X2), the above-mentioned oxidation method or unevenness method is applied to the surface of the base material (Y2) on the side where the pressure-sensitive adhesive layer is laminated. Such as surface treatment, easy adhesion treatment, or primer treatment may be performed.
Further, in the adhesive laminate used in one aspect of the present invention, from the viewpoint of suppressing the residue of the adhesive layer (X2) from adhering to the cutting object and / or the ground object, the surface such as a semiconductor wafer having bumps or the like. The pressure-sensitive adhesive sheet (II) is based on the pressure-sensitive adhesive sheet (II) from the viewpoint of excellent followability to a work object having large irregularities and from the viewpoint of excellent stability of the adhesive force of the pressure-sensitive adhesive layer (X2) over time. It is preferable to have an intermediate layer (Z2) between the material (Y2) and the pressure-sensitive adhesive layer (X2).
Further, for example, the surface of the base material (Y2) on the pressure-sensitive adhesive layer (X2) side may be subjected to antistatic treatment. When the intermediate layer (Z2) is provided, the surface of the base material (Y2) on the intermediate layer (Z2) side may be subjected to antistatic treatment.

The base material (Y2) is preferably a non-thermally expandable base material from the viewpoint that it can be easily separated collectively at the interface P with the pressure-sensitive adhesive sheet (I) with a slight force.
Further, from the viewpoint of maintaining good adhesion to the adherend before and after the heat treatment, the pressure-sensitive adhesive layer (X2) is also preferably a non-thermally expandable pressure-sensitive adhesive layer.
Further, the intermediate layer (Z2) is also preferably a non-thermally expandable layer.
Therefore, the volume change rate (%) of the base material (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) calculated from the above formula is independently less than 5%, but is preferable. Is less than 2%, more preferably less than 1%, even more preferably less than 0.1%, even more preferably less than 0.01%. More preferably, the base material (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) do not contain heat-expandable particles.
Hereinafter, the base material (Y2), the pressure-sensitive adhesive layer (X2), and the intermediate layer (Z2) will be described.

<Base material (Y2)>
Examples of the material for forming the base material (Y2) include the same materials as those for forming the non-thermally expandable base material layer (Y1-2) described above.
The base material (Y2) preferably contains a resin, and it is more preferable that a resin layer containing the resin is formed at least on the surface of the base material (Y2) on the side where the pressure-sensitive adhesive sheet (I) is laminated. It is more preferable that the base material (Y2) is a resin film or a resin sheet.
Further, among the resin films or resin sheets, in the grinding of the object to be processed in the step (4), the object to be processed can be stably held even when the object to be processed is extremely thinly ground. From the above viewpoint, a polyethylene film, a polypropylene film, an ethylene-vinyl acetate copolymer (EVA) film, and a polyethylene terephthalate film are preferable, and an ethylene-vinyl acetate copolymer (EVA) film is more preferable.
The above-mentioned resin film or resin sheet may contain known fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts and the like.
Further, the resin film or the resin sheet may be transparent, or may be colored or metal-deposited as desired.
Further, from the viewpoint of enabling easy separation at the interface P with a slight force after the heat treatment for separation, the surface of the base material (Y2) to be laminated on the pressure-sensitive adhesive sheet (I) is peeled off. May be good.

Further, the base material (Y2) has a viewpoint that it is easy to prevent misalignment when the object to be processed is attached to the pressure-sensitive adhesive layer (X2), and when the object to be processed is attached, the adhesive layer ( from the viewpoint of those likely to prevent excessive sinking of the X2), it preferably has a storage elastic modulus E at 23 ℃ '(23) is 1.0 × ¹⁰ 6 Pa or more.

The base material (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range, but from the above viewpoint, the content of the thermally expandable particles in the base material (Y2) is , The smaller the number, the better.
The content of the heat-expandable particles in the base material (Y2) is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than the total mass (100% by mass) of the base material (Y2). It is less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass. More preferably, the base material (Y2) does not contain thermally expandable particles.

The thickness of the base material (Y2) is preferably 5 to 500 μm, more preferably 15 to 300 μm, and even more preferably 20 to 200 μm.
When the thickness of the base material (Y2) is 5 μm or more, it is easy to make it excellent in deformation resistance (dimensional stability) at high temperature. On the other hand, if the thickness of the base material is 500 μm or less, the pressure-sensitive adhesive sheet (II) due to vibration when at least one of cutting and grinding is performed on the object to be processed attached to the pressure-sensitive adhesive sheet (II). Since it is possible to suppress the deformation of the material, it is easy to improve the processing accuracy such as the film thickness accuracy.

<Adhesive layer (X2)>
The pressure-sensitive adhesive layer (X2) contained in the resin film-forming sheet (II) can be formed by using the above-mentioned pressure-sensitive adhesive composition (x1). It is the same as the pressure-sensitive adhesive composition (x1).

Here, in one aspect of the present invention, the pressure-sensitive adhesive layer (X2) is derived from a pressure-sensitive adhesive composition organism containing an energy ray-curable pressure-sensitive adhesive resin in which a polymerizable functional group is introduced into a side chain as a pressure-sensitive adhesive resin. A pressure-sensitive adhesive composition containing an energy ray-curable acrylic polymer (B) (hereinafter, also referred to as “acrylic polymer (B)” or “component (B)”), which is preferably a formed layer. It is more preferably a layer formed from.
The pressure-sensitive adhesive layer (X2) formed from the pressure-sensitive adhesive composition has an excellent adhesive strength capable of sufficiently holding an object to be processed before irradiation with energy rays, but the adhesive strength decreases after irradiation with energy rays. To do. Therefore, the processed product can be easily separated from the adhesive sheet (II).

The content of the component (B) in the pressure-sensitive adhesive composition is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass, based on the total amount (100% by mass) of the pressure-sensitive adhesive composition. % Or more, preferably 99.9% by mass or less, more preferably 99.0% by mass or less, still more preferably 98.0% by mass or less.

The thickness of the pressure-sensitive adhesive layer (X2) is such that it has good adhesive strength and has good followability to a work object having a large difference in surface irregularities such as a semiconductor wafer having bumps and the like. It is preferably 1 to 100 μm, more preferably 1 to 75 μm, and further preferably 1 to 50 μm.

Further, when the pressure-sensitive adhesive composition, which is a material for forming the pressure-sensitive adhesive layer (X2), contains an energy ray-curable adhesive resin such as an energy ray-curable acrylic polymer (B), a cross-linking agent or a cross-linking agent or It preferably contains a photopolymerization initiator.
Examples of the cross-linking agent include the same as those blended in the acrylic resin described above, and the content range is as described above, but the adhesive layer (X2) is processed by increasing the gel content. From the viewpoint of suppressing the formation of adhesive residue on the processed product when the product is separated, it is preferably 0.1 to 20 parts by mass, more preferably 0 parts by mass, based on 100 parts by mass of the adhesive resin having a functional group. It is 5 to 15 parts by mass, more preferably 1.0 to 10 parts by mass.
Examples of the photopolymerization initiator include the same as those blended in the solvent-free resin composition (y1) described above, and the range of the content is also as described above.
Moreover, you may contain other additives other than these.
Hereinafter, the energy ray-curable acrylic polymer (B) contained in the pressure-sensitive adhesive composition will be described.

(Component (B): Energy ray-curable acrylic polymer (B))
The energy ray-curable acrylic polymer (B) used in one embodiment of the present invention is an acrylic in which a polymerizable functional group is introduced into the side chain and / or the main chain of the non-energy ray-curable acrylic polymer. It is a system copolymer.
The non-energy ray-curable acrylic polymer may be, for example, an acrylic polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, or a (meth) acrylate having a cyclic structure. Examples thereof include acrylic polymers having a structural unit from which they are derived.
The polymerizable functional group is as described above, but a (meth) acryloyl group is preferable from the viewpoint of ease of introduction into a non-energy ray-curable acrylic polymer.

The mass average molecular weight (Mw) of the component (B) is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,200,000, more preferably 250,000 to 1,000,000, still more preferably 300,000 to 900,000, and even more. It is preferably 350,000 to 800,000.

The component (B) is an alkyl (meth) acrylate (b1') having an alkyl group having 1 to 18 carbon atoms (hereinafter, from the viewpoint of forming a pressure-sensitive adhesive sheet whose adhesive strength can be effectively reduced by irradiation with energy rays). , A structural unit (b1) derived from a "monomer (b1')") and a functional unit (b2') derived from a functional group-containing monomer (b2') (hereinafter, also referred to as "monomer (b2')"). It is preferable to contain an energy ray-curable acrylic copolymer (B1) obtained by reacting the acrylic copolymer (B0) having the polymer with the polymerizable compound (Xb), and the energy ray-curable acrylic copolymer. It is more preferably a copolymer (B1).
The form of copolymerization of the acrylic copolymers (B0) and (B1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.

The content of the acrylic copolymer (B1) is preferably 70 to 100% by mass, more preferably 80 to 100% with respect to the total amount (100% by mass) of the component (B) contained in the pressure-sensitive adhesive composition. It is by mass, more preferably 90 to 100% by mass, and even more preferably 100% by mass.

The number of carbon atoms of the alkyl group contained in the monomer (b1') is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 8, and even more preferably 1 to 6.
Examples of the monomer (b1') include those exemplified as the above-mentioned monomer (a1'), but butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate is preferable, and butyl (meth) acrylate is more preferable.

The content of the structural unit (b1) in the acrylic copolymer (B0) is the total structural unit (100 mass) of the acrylic copolymer (B0) from the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive layer to be formed. %), It is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, still more preferably 70 to 98% by mass, and even more preferably 80 to 96% by mass.

Examples of the monomer (b2') include those exemplified as the above-mentioned monomer (a2'), but one or more selected from a hydroxyl group-containing monomer, a carboxy group-containing monomer, and an epoxy group-containing monomer is preferable, and a hydroxyl group-containing monomer is preferable. Is more preferable, and 2-hydroxyethyl (meth) acrylate is further preferable.

The content of the structural unit (b2) in the acrylic copolymer (B0) is preferably 0.5 to 40% by mass with respect to the total structural units (100% by mass) of the acrylic copolymer (B0). , More preferably 1 to 30% by mass, still more preferably 2 to 25% by mass, and even more preferably 3 to 15% by mass.
When the content of the structural unit (b2) is 0.5% by mass or more, the content of the structural unit (b2) having a functional group serving as a reaction point with the polymerizable compound (Xb) can be sufficiently secured, and the energy can be sufficiently secured. Since a highly curable pressure-sensitive adhesive layer (X2) can be formed by irradiating with a line, the cut material and / or the ground product is peeled off from the pressure-sensitive adhesive layer (X2). It can be peeled off while preventing the generation of the residue of the adhesive layer (X2) on the surface.
Further, when the content of the structural unit (b2) is 40% by mass or less, a sufficient pot life can be secured when the solution of the pressure-sensitive adhesive composition is applied to form the pressure-sensitive adhesive layer (X2). it can.
The polymerizable compound (Xb) is polymerizable with a substituent (hereinafter, also referred to as “reactive functional group”) capable of binding to a functional group in the structural unit (b2) of the acrylic copolymer (B0). It means a compound having a functional group.

The acrylic copolymer (B0) may have a structural unit (b3) derived from a monomer (b3') other than the above-mentioned monomers (b1') and (b2').
Examples of the other monomer (b3') include those exemplified as the above-mentioned monomer (a3').

The content of the structural unit (b3) in the acrylic copolymer (B0) is preferably 0 to 20% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (B0). It is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 1% by mass.
The above-mentioned monomers (b1') to (b3') may be used alone or in combination of two or more.

The energy ray-curable acrylic copolymer (B1) is obtained by reacting the acrylic copolymer (B0) having the above-mentioned structural units (b1) and (b2) with the polymerizable compound (Xb). Be done.
Examples of the polymerizable compound (Xb) include those exemplified as the above-mentioned polymerizable compound (Xa). Among these, the polymerizable compound (Xb) has a reactive functional group and 1 to 5 polymerizable functional groups per molecule. It is preferably a compound having.
Examples of the reactive substituent include an isocyanate group, a carboxyl group, an epoxy group and the like, and an isocyanate group is preferable.
As described above, examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group and the like, and a (meth) acryloyl group is preferable.
As the specific polymerizable compound (Xb), (meth) acryloyloxyethyl isocyanate is preferable.
The polymerizable compound (Xb) may be used alone or in combination of two or more.

Regarding the relationship between the number of functional groups of the acrylic copolymer (B0) and the blending amount of the polymerizable compound (Xb) in the acrylic copolymer (B1), the acrylic copolymer (B1) has an appropriate adhesive strength before irradiation with energy rays. From the viewpoint of obtaining an adhesive sheet whose adhesive strength can be effectively reduced after irradiation with energy rays, the value of α calculated from the following formula (1) is preferably 0.5 to 50, more preferably 1. It is 0 to 40, more preferably 1.2 to 35, and even more preferably 1.5 to 30.
The value of α corresponds to the number of polymerizable functional groups of the acrylic copolymer (B1).
Equation (1): α = _{[P B]} × _{[Q B]} × _{[R B]} / 100
(In the formula (1), [P _B ] indicates the content of the structural unit (b2) with respect to 100 parts by mass of all the structural units of the acrylic copolymer (B0). [Q _B ] is the acrylic copolymer weight. for functional group 100 equivalents from the functional group-containing monomer polymer of (B0) has,. shows the equivalent weight of the polymerizable compound (Xb) [R _B] shows the polymerizable functional groups of the polymerizable compound (Xb) has .)

<Intermediate layer (Z2)>
In one aspect of the present invention, the intermediate layer (Z2) is a composition for forming an intermediate layer (z2) containing a non-energy ray-curable acrylic polymer (C) and an energy ray-curable acrylic polymer (D). ) Is formed from.
By providing the intermediate layer (Z2), the pressure-sensitive adhesive sheet (II) has excellent followability to a work object having large surface irregularities such as a semiconductor wafer having bumps. Therefore, when at least one of cutting and grinding is performed on the work object to which the adhesive sheet (II) is attached, damage to the work object is suppressed, and cutting chips, grinding chips, cutting water, and cutting water are suppressed. It is possible to prevent the grinding water or the like from entering the surface to be attached to the adhesive sheet (II) of the object to be processed.
The intermediate layer (Z2) may or may not have adhesiveness.

The thickness of the intermediate layer (Z2) is appropriately selected depending on the degree of unevenness of the object to be processed, for example, when the object to be processed is a semiconductor wafer or a semiconductor chip, the height of the bumps of the semiconductor wafer or the semiconductor chip. However, it is preferably 10 to 800 μm, more preferably 15 to 600 μm, and even more preferably 20 to 400 μm.
When the thickness of the intermediate layer (Z2) is 10 μm or more, it is possible to improve the followability to a work object having a large difference in unevenness. On the other hand, when the thickness of the intermediate layer is 800 μm or less, it is easy to suppress the deformation of the adhesive sheet (II).

The intermediate layer forming layer composition (z2), which is a material for forming the intermediate layer (Z2), provides adhesion between the intermediate layer (Z2) of the pressure-sensitive adhesive sheet (II) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays. As a good thing, when the cut object and / or the ground object is peeled off from the adhesive sheet (II), the adhesive layer (X2) is broken or the adhesive layer (X2) on the surface of the cut object and / or the ground object is formed. From the viewpoint of suppressing the generation of residues, a non-energy ray-curable acrylic polymer (C) (hereinafter, also referred to as "acrylic polymer (C)" or "component (C)") and mass average molecular weight. It is preferable to contain an energy ray-curable acrylic polymer (D) of 50,000 to 250,000 (hereinafter, also referred to as “acrylic polymer (D)” or “component (D)”).
Further, from the viewpoint of further improving the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays, the content of the component (D) in the intermediate layer forming composition (z2) is With respect to 100 parts by mass of the component (C), it is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 37 parts by mass or more, still more preferably 40 parts by mass or more.
Further, in one aspect of the present invention, (D) in the intermediate layer forming composition (z2) from the viewpoint of suppressing the exudation of a part of the intermediate layer (Z2) from the end portion of the pressure-sensitive adhesive sheet (II). The content of the component () is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, and further preferably 130 parts by mass or less with respect to 100 parts by mass of the component (C).

The total content of the component (C) and the component (D) in the intermediate layer forming composition (z2) is preferably 70% by mass with respect to the total amount (100% by mass) of the intermediate layer forming composition (z2). % Or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99.9% by mass or less, more preferably 99.0% by mass or less, still more preferably 98.0% by mass. It is as follows.

The intermediate layer forming composition (z2) preferably further contains a photopolymerization initiator and a cross-linking agent in addition to the above components (C) and (D). Moreover, you may contain other additives other than these.
Examples of the cross-linking agent include those similar to those blended in the above-mentioned acrylic resin, and the range of the content is also as described above.
Examples of the photopolymerization initiator include the same as those blended in the solvent-free resin composition (y1) described above, and the range of the content is also as described above.
Moreover, you may contain other additives other than these.
Hereinafter, the non-energy ray-curable acrylic polymer (C) and the energy ray-curable acrylic polymer (D) contained in the intermediate layer forming composition (z2) will be described.

(Component (C): Non-energy ray-curable acrylic polymer (C))
Examples of the non-energy ray-curable acrylic polymer (C) include a polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and having a cyclic structure (meth). Examples thereof include polymers having a structural unit derived from acrylate.

The mass average molecular weight (Mw) of the component (C) is preferably 300,000 to 1,500,000, more preferably 350,000 to 1,300,000, more preferably 400,000 to 1,200,000, still more preferably 400,000 to 1,100,000. It is preferably 450,000 to 900,000.

The component (C) is an alkyl (meth) acrylate (c1') having an alkyl group having 1 to 18 carbon atoms (hereinafter, also referred to as "monomer (c1')" from the viewpoint of compatibility with the component (D). ) And an acrylic copolymer (C1) having a functional group-containing monomer (c2') (hereinafter, also referred to as "monomer (c2')"). It is preferably contained, and more preferably an acrylic copolymer (C1).
The form of copolymerization of the acrylic copolymer (C1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.

The content of the acrylic copolymer (C1) is preferably 70 to 100% by mass, based on the total amount (100% by mass) of the component (C) contained in the intermediate layer forming composition (z2). It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 100% by mass.

The number of carbon atoms of the alkyl group contained in the monomer (c1') is more preferably 4 to 12, still more preferably 4 to 8, still more preferably 4 to 6, from the viewpoint of compatibility with the component (D). ..

Examples of the monomer (c1') include those similar to the above-mentioned monomer (a1').
Among these, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.

The content of the structural unit (c1) in the acrylic copolymer (C1) is preferably 50 to 99.5% by mass with respect to the total structural units (100% by mass) of the acrylic copolymer (C1). , More preferably 60 to 99% by mass, still more preferably 70 to 95% by mass, and even more preferably 80 to 93% by mass.
When the content of the structural unit (c1) is 50% by mass or more, it is preferable because an adhesive sheet having a large unevenness difference and having good followability to a work object can be obtained.
Further, when the content of the structural unit (c1) is 99.5% by mass or less, the content of the structural unit (c2) can be sufficiently secured and the compatibility with the component (D) can be improved. Therefore, it is preferable.

Further, the acrylic copolymer (C1) is an alkyl having an alkyl group having 4 or more carbon atoms (preferably 4 to 12, more preferably 4 to 8, still more preferably 4 to 6) as a constituent unit (c1). It is preferable to have a structural unit (c11) derived from (meth) acrylate.
The content ratio of the structural unit (c11) in the structural unit (c1) is preferably 60% by mass or more with respect to the total amount (100% by mass) of the structural unit (c1) contained in the acrylic copolymer (C1). It is more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 85% by mass or more, and preferably 100% by mass or less.

Examples of the functional group contained in the monomer (c2') include the same functional groups as those contained in the monomer (a2') described above.
As the specific monomer (c2'), the same monomer (a2') as described above can be mentioned.
Among these, one or more selected from a hydroxyl group-containing monomer, a carboxy group-containing monomer, and an epoxy group-containing monomer are preferable, and a carboxy group-containing monomer is more preferable.
Specific examples of the hydroxyl group-containing monomer, the carboxy group-containing monomer, and the epoxy group-containing monomer are the same as those of the above-mentioned monomer (a2').

The content of the structural unit (c2) in the acrylic copolymer (C1) is preferably 0.5 to 50% by mass with respect to the total structural units (100% by mass) of the acrylic copolymer (C1). , More preferably 1 to 40% by mass, still more preferably 5 to 30% by mass, and even more preferably 7 to 20% by mass.
When the content of the structural unit (c2) is 0.5% by mass or more, the compatibility with the component (D) can be improved, which is preferable.
Further, when the content of the structural unit (c2) is 50% by mass or less, it is preferable that the pressure-sensitive adhesive sheet has good followability to an adherend having a large difference in unevenness.

The acrylic copolymer (C1) may have a structural unit (c3) derived from a monomer (c3') other than the above-mentioned monomers (c1') and (c2').
Examples of the other monomer (c3') include those similar to the above-mentioned monomer (a3').

The content of the structural unit (c3) in the acrylic copolymer (C1) is preferably 0 to 30% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (C1). It is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass.
The above-mentioned monomers (c1') to (c3') may be used alone or in combination of two or more.

(Component (D): Energy ray-curable acrylic polymer (D))
The energy ray-curable acrylic polymer (D) is an acrylic polymer in which a polymerizable functional group is introduced into a non-energy ray-curable acrylic polymer.
The polymerizable functional group is introduced into the main chain and / or side chain of the non-energy ray-curable acrylic polymer.
By containing the component (D) in the intermediate layer, when the energy ray is irradiated, the component (D) and the component (B) in the pressure-sensitive adhesive layer (X2) react and bond with each other to form a pressure-sensitive adhesive sheet (II). ), It is considered that the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) is improved. Further, it is considered that the pressure-sensitive adhesive layer (X2) and the intermediate layer (Z2) are hardened, and the adhesive residue can be suppressed. Therefore, it is possible to suppress the residual residue of the pressure-sensitive adhesive layer (X2) when the cut product and / or the ground product is peeled from the pressure-sensitive adhesive sheet (II).

Examples of the non-energy ray-curable acrylic polymer include an acrylic polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a (meth) acrylate having a cyclic structure. Examples thereof include acrylic polymers having a structural unit from which they are derived.

The polymerizable functional group may be a group containing an energy ray-polymerizable carbon-carbon double bond, and examples thereof include a (meth) acryloyl group and a vinyl group. However, it is easy to introduce an energy ray-polymerizing group. From the viewpoint of existence, a (meth) acryloyl group is preferable.
The energy ray-polymerizable group may be bonded to the main chain or side chain of the non-energy ray-curable acrylic polymer via an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or the like.

The mass average molecular weight (Mw) of the component (D) is preferably 50,000 to 250,000, more preferably 60,000 to 220,000, still more preferably 70,000 to 200,000, and even more preferably 80,000 to 180,000. Even more preferably, it is 85,000 to 150,000.
When the Mw of the component (D) is less than 50,000, the stability of the obtained adhesive sheet with time tends to be inferior. That is, when the pressure-sensitive adhesive sheet is stored for a long period of time, a part of the component (D) moves into the pressure-sensitive adhesive layer, the adhesive strength of the pressure-sensitive adhesive sheet becomes unstable, and after irradiation with energy rays, the pressure-sensitive adhesive layer ( X2) tends to cure excessively. As a result, when the adhesive sheet is used after long-term storage, or when it is left for a long period of time with the object to be processed attached, the intermediate layer (Z2) and the adhesive layer (X2) adhere to each other after irradiation with energy rays. Due to insufficient properties, the pressure-sensitive adhesive layer (X2) may be broken when the pressure-sensitive adhesive sheet is peeled off, or the residue of the pressure-sensitive adhesive layer (X2) may adhere to the cut object and / or the ground product.
On the other hand, when the Mw of the component (D) exceeds 250,000, the adhesion between the intermediate layer (Z2) and the adhesive layer (X2) after irradiation with energy rays tends to be inferior, and the cut object / searched object is a pressure-sensitive adhesive sheet (II). ), The adhesive layer (X2) may be broken or the residue of the adhesive layer (X2) may adhere to the cut object and / or the ground object.

As the component (D), from the viewpoint of forming an adhesive sheet having excellent stability over time, and adhesion with improved adhesion between the formed intermediate layer (Z2) and the adhesive layer (X2) after irradiation with energy rays. From the viewpoint of making a sheet, it contains a structural unit (d1) and a functional group derived from an alkyl (meth) acrylate (d1') having an alkyl group having 1 to 18 carbon atoms (hereinafter, also referred to as "monomer (d1')"). Obtained by reacting an acrylic copolymer (D0) having a structural unit (d2) derived from a monomer (d2') (hereinafter, also referred to as "monomer (d2')") with a polymerizable compound (Xd). It is preferable to contain the energy ray-curable acrylic copolymer (D1) to be obtained, and more preferably the energy ray-curable acrylic copolymer (D1).
The form of copolymerization of the acrylic copolymers (D0) and (D1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.

The content of the acrylic copolymer (D1) is preferably 70 to 100% by mass, based on the total amount (100% by mass) of the component (D) contained in the intermediate layer forming composition (z2). It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 100% by mass.

The number of carbon atoms of the alkyl group contained in the monomer (d1') is more preferably 4 to 12, still more preferably 4 to 8, and even more preferably 4 to 6.
Examples of the monomer (d1') include those exemplified as the above-mentioned monomer (a1').
Among these, butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate is preferable, and butyl (meth) acrylate is more preferable.

The content of the structural unit (d1) in the acrylic copolymer (D0) is preferably 50 to 99% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer (D0). It is preferably 55 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 85% by mass.
When the content of the structural unit (d1) is 50% by mass or more, the shape of the intermediate layer (Z2) to be formed can be sufficiently maintained, which is preferable.
Further, when the content of the structural unit (d1) is 99% by mass or less, the content of the structural unit (d2) having a functional group serving as a reaction point with the polymerizable compound (Xd) can be sufficiently secured and formed. It is preferable because the adhesion between the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays can be improved.

Examples of the monomer (d2') include those exemplified as the above-mentioned monomer (a2'), but one or more selected from a hydroxyl group-containing monomer, a carboxy group-containing monomer, and an epoxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is preferable. Is more preferable, hydroxyacrylic (meth) acrylate is further preferable, and 2-hydroxyethyl (meth) acrylate is even more preferable.

The content of the structural unit (d2) in the acrylic copolymer (D0) is preferably 1 to 50% by mass, more preferably 1 to 50% by mass, based on the total structural units (100% by mass) of the acrylic copolymer (D0). It is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass.
When the content of the structural unit (d2) is 1% by mass or more, the polymerizability is sufficient to improve the adhesion between the formed intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) after irradiation with energy rays. It is preferable because a reaction point with the compound (Xd) can be secured.
Further, when the content of the structural unit (d2) is 50% by mass or less, the shape of the formed intermediate layer (Z2) can be sufficiently maintained, which is preferable.

The acrylic copolymer (D0) may have a structural unit (b3) derived from a monomer (d3') other than the above-mentioned monomers (d1') and (d2').
Examples of the other monomer (d3') include those exemplified as the above-mentioned monomer (a3').

The content of the structural unit (d3) in the acrylic copolymer (D0) is preferably 0 to 30% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (D0). It is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass.
The above-mentioned monomers (d1') to (d3') may be used alone or in combination of two or more.

In the energy ray-curable acrylic copolymer (D1), the functional group in the structural unit (d2) of the acrylic copolymer (D0) reacts with the polymerizable compound (Xd) to form a polymerizable compound. The polymerizable functional group of (Xd) is introduced into at least one of the main chain and the side chain of the acrylic copolymer (D0).

The polymerizable compound (Xd) is not particularly limited as long as it is a compound having a polymerizable functional group and has a reactive functional group.
Among the polymerizable compounds (Xd), it is preferable that the compound has the above-mentioned reactive substituents and 1 to 5 polymerizable functional groups per molecule.
Examples of the reactive substituent include an isocyanate group, a carboxyl group, an epoxy group and the like, and an isocyanate group is preferable.
As described above, examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group and the like, and a (meth) acryloyl group is preferable.

Specific examples of the polymerizable compound (Xd) include the same compounds as the above-mentioned polymerizable compound (Xb).
The polymerizable compound (Xd) may be used alone or in combination of two or more.
Among these, from the viewpoint that the compound has an isocyanate group suitable as the reactive substituent and the distance between the acrylic copolymer (D0) and the energy ray-polymerizable group is appropriate, it is a compound. (Meta) acryloyloxyethyl isocyanate is preferred.

Regarding the relationship between the number of functional groups of the acrylic copolymer (D0) and the blending amount of the polymerizable compound (Xd) in the acrylic copolymer (D1), the intermediate layer (Z2) and the pressure-sensitive adhesive layer (X2) are formed. ), The value of β calculated from the following formula (2) is preferably 1 to 50, more preferably 2 to 40, still more preferably 3 to 35, from the viewpoint of improving the adhesion after irradiation with energy rays. Even more preferably, it is 5 to 30.
The value of β corresponds to the number of energy ray-polymerizable groups of the acrylic copolymer (D1).
Equation (2): β = [P _d ] × [Q _d ] × [R _d ] / 100
(In the formula (2), [P _d ] indicates the content of the structural unit (d2) with respect to 100 parts by mass of all the structural units of the acrylic copolymer (D0). [Q _d ] is the acrylic common weight. The equivalent amount of the polymerizable compound (Xd) to 100 equivalents of the functional group derived from the functional group-containing monomer of the coalescence (D0) is shown. [R _d ] indicates the number of polymerizable functional groups of the polymerizable compound (Xd). .)

(Other additives contained in the composition for forming an intermediate layer)
The intermediate layer forming composition (z2) may contain other additives as long as the effects of the present invention are not impaired.
Examples of other additives include antioxidants, softeners (plasticizers), fillers, rust preventives, pigments, dyes, tackifiers and the like.
When these additives are contained, the content of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the component (A). is there.

<Release material>
In the adhesive laminate of one aspect of the present invention, a release material may be further laminated on the surfaces of the pressure-sensitive adhesive layers (X1) and (X2) to be attached to the object to be processed.
Examples of the release material include a release sheet that has undergone double-sided release treatment, a release sheet that has undergone single-sided release treatment, and the like, in which a release agent is applied onto a base material for the release material.

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

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

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

<Physical characteristics of adhesive sheet (II)>
In one aspect of the present invention, the adhesive sheet (II) preferably satisfies one or more of the following requirements (α) to (γ) from the viewpoint of facilitating cutting and grinding in the step (4), and the following requirements. It is more preferable to satisfy any two of (α) to (γ), and it is further preferable to satisfy all of the requirements (α) to (γ).
-Requirement (α): Young's modulus of the base material (Y2) is 1.0 MPa or more.
-Requirement (β): The thickness of the base material (Y2) is 5 μm or more.
-Requirement (γ): The storage elastic modulus G'(23 ° C.) of the pressure-sensitive adhesive layer (X2) is 0.10 MPa or more.
From the viewpoint of facilitating cutting and grinding in the step (4), the Young's modulus of the base material (Y2) defined by the requirement (α) is preferably 1.0 to 1000 MPa, preferably 1.5 to 1000 MPa. It is more preferably 800 MPa, and even more preferably 2.0 to 500 MPa.
Further, from the viewpoint of facilitating cutting and grinding in the step (4), the thickness of the base material (Y2) defined by the requirement (β) is preferably 5 to 250 μm, preferably 10 to 230 μm. Is more preferable, and 20 to 210 μm is even more preferable.
Further, from the viewpoint of facilitating cutting and grinding in the step (4), the storage elastic modulus G'(23 ° C.) of the pressure-sensitive adhesive layer (X2) defined by the requirement (γ) is 0.10 to 1 MPa. It is preferably 0.12 to 0.9 MPa, more preferably 0.14 to 0.8 MPa.

[Each process of manufacturing method of processed products]
Next, each step of the method for producing a processed product of the present invention will be described in detail.
The method for producing a processed product of the present invention has a base material (Y1) and an adhesive layer (X1), and one of the layers contains thermally expandable particles having a thermal expansion start temperature (t). The sheet (I) and the pressure-sensitive adhesive sheet (II) having the base material (Y2) and the pressure-sensitive adhesive layer (X2) are provided, and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. It is a method of manufacturing a processed product which has been subjected to at least one of cutting and grinding using the adhesive laminate.
The following steps (1) to (3) are performed in this order.
Step (1): A step of attaching the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and attaching the object to be processed to the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate. -Step (2): A step of performing one or more processing on the processing object-Step (3): By heating the heat-expandable particles at a thermal expansion start temperature (t) or higher, the processing object is adhered to the adhesive. The adhesive laminate is separated at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) while maintaining the state of being attached to the surface of the adhesive layer (X2) of the adhesive laminate. Steps to be performed Further, it has the following step (4).
Step (4): A step of performing at least one of cutting and grinding on the surface of the object to be processed opposite to the surface to which the adhesive layer (X2) is attached. It is carried out in at least one of the following (X) and (Y).
(X): Performed in the step (2) as the one or more processes (Y): Performed after the step (3)

In the production method of the present invention, the above-mentioned adhesive laminate is used. Specifically, the surface of the adhesive layer (X1) of the adhesive sheet (I) of the adhesive laminate is attached to the support, and the adhesive layer (X2) of the adhesive sheet (II) of the adhesive laminate is attached. It is used by sticking the object to be processed on the surface. Therefore, a predetermined process can be performed with the object to be processed fixed to the support. Moreover, after the predetermined processing is performed, the adhesive sheet (II) to which the processed object to which the predetermined processing has been applied is attached can be easily separated from the adhesive sheet (I) at once with a slight force. can do. That is, the pressure-sensitive adhesive sheet (II) to which the processed object subjected to the predetermined processing is attached can be easily separated from the support. Therefore, the processed object that has undergone the predetermined processing can be used in the next step without being attached to a new pressure-sensitive adhesive sheet.
Hereinafter, each step of the production method of the present invention will be described with reference to FIGS. 4 and 5 as appropriate.

<Process (1)>
4 (a) and 5 (a) are schematic cross-sectional views showing a state in which the object to be processed is attached to the support via the adhesive laminate.
In the step (1), as shown in FIGS. 4 (a) and 5 (a), the objects to be processed 60 and 70 are attached to the support 50 via the adhesive laminate 1a of the first aspect. The support, the adhesive laminate, and the object to be processed are laminated in this order.
Although FIGS. 4 and 5 show an example in which the adhesive laminate 1a shown in FIG. 1A is used, the adhesive laminate of the present invention having another configuration is also used. Similarly, the support, the adhesive laminate, and the object to be processed are laminated in this order.

As shown in FIGS. 4 (a) and 5 (a), in the step (1), the objects to be processed 60 and 70 are attached to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) contained in the pressure-sensitive adhesive laminate. Then, the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the support 50 of the pressure-sensitive adhesive laminate are attached.

Examples of the object to be processed to be attached to the adhesive laminate include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panel substrates.
Further, the object to be processed may be a semiconductor wafer or the like having a notch groove formed on the surface, and the surface side on which the notch groove is formed may be bonded to the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II). .. Further, the object to be processed may be a semiconductor wafer or the like in which a modified region is formed in advance by irradiation with laser light. In these cases, by performing grinding in step (4), the cutting groove or the modified region becomes the division starting point, and the object to be processed can be divided.
That is, when the object to be processed is a semiconductor wafer in which a notch groove is formed on the surface, the manufacturing method of one aspect of the present invention comprises the following step (1-C) in step (1) and said step (4). ) Is the following step (4-C).
Step (1-C): The surface of the adhesive layer (X1) of the adhesive laminate is attached to the support, and the semiconductor wafer is cut into the surface of the adhesive layer (X2) of the adhesive laminate. Step / Step (4-C) of attaching the grooved surface: A process of grinding the surface of the semiconductor wafer opposite to the attachment surface with the pressure-sensitive adhesive layer (X2). In the case of a semiconductor wafer having a modified region serving as a division starting point, in the manufacturing method of one aspect of the present invention, step (4) is the following step (4-A).
Step (4-A): A step of grinding the surface of the semiconductor wafer on the side opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached.

The support is used in step (2) to fix the object to be processed and improve the accuracy of processing.
The support is preferably attached to the entire surface of the adhesive surface of the adhesive layer (X1) of the adhesive laminate.
Therefore, the support is preferably plate-shaped. Further, as shown in FIGS. 4 and 5, the area of the adhesive surface 122a of the adhesive layer (X1) and the surface of the support 50 on the side to be attached is equal to or larger than the area of the adhesive surface 122a of the adhesive layer (X1). Is preferable.

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

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

The temperature condition in the step (1) may be less than the expansion start temperature (t) of the thermally expandable particles.

<Process (2)>
In the step (2), one or more processes are performed on the object to be processed, which is attached to the pressure-sensitive adhesive layer (X2) of the adhesive laminate of the present invention in the step (1).
The processing performed in the step (2) includes, for example, a sealing process using a resin on the processing target, a processing of forming a modified region as a division starting point on the processing target, a circuit forming process, an etching process, and a plating process. , Sputtering treatment, vapor deposition treatment, protective film forming treatment, laminating treatment using a separately prepared adhesive sheet, and the like.
Further, the processing performed in the step (2) may be at least one of cutting and grinding of the object to be processed.
That is, the processing performed in the step (2) may be a process including at least one of a step of cutting the object to be processed and a process of grinding, or a step of cutting the object to be processed and a step of grinding. It may be a process that does not include.
The temperature condition in the step (2) may be less than the expansion start temperature (t) of the heat-expandable particles as in the step (1).
Hereinafter, as step (2), when a process (step (2-A)) of forming a modified region serving as a division starting point is performed on the object to be processed, a sealing process (step (2)) using a resin is applied to the object to be processed. -B)) will be described as an example.

(Step (2-A))
The step (2-A) is a step in which the object to be processed is a semiconductor wafer and a modified region serving as a division starting point is formed on the semiconductor wafer.
Specifically, as shown in FIG. 4B, the surface of the semiconductor wafer opposite to the surface to which the adhesive sheet (II) is attached is the laser light incident surface, and the laser light condensing point is the semiconductor wafer. By irradiating the laser beam so as to be inside, the modified region 71 by multiphoton absorption or the like is formed. The modified region 71 functions as a division starting point of the semiconductor wafer by performing grinding in the step (4).
In the production example shown in FIG. 4, the step (4) is performed after the step (3), but one of the one or more processes in the step (2) after the step (2-A). The grinding of the step (4) may be carried out. In this case, the fragmented semiconductor wafer can be used in the next step in a state of being attached to the pressure-sensitive adhesive sheet (II) without separating the fragmented semiconductor wafer from the pressure-sensitive adhesive sheet (II).
That is, in the manufacturing method of one aspect of the present invention, the object to be processed is a semiconductor wafer, and one or more processes in the step (2) include the following steps (2-A).
Step (2-A): Step of forming a modified region serving as a division starting point on the semiconductor wafer Step (4) is the following step (4-A).
Step (4-A): A step of grinding the surface of the semiconductor wafer opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached. Or it is carried out in (YA).
(XA): Performed after step (2-A) as one or more processes (YA): Performed after step (3)

(Step (2-B))
In the step (2-B), the object to be processed is a semiconductor chip, and the semiconductor chip and the peripheral portion of the adhesive surface of the pressure-sensitive adhesive layer (X2) are covered with a sealing material. This is a step of curing the encapsulant to obtain a cured encapsulant obtained by encapsulating the semiconductor chip in the cured encapsulant.

As shown in FIG. 5, when the manufacturing method of the present invention has a step (2-B), the semiconductor chip 60 is used as a processing target in the step (1).
As the semiconductor chip 60, a conventionally known one can be used, and an integrated circuit composed of circuit elements such as a transistor, a resistor, and a capacitor is formed on the circuit surface thereof.
Then, it is preferable that the circuit surface of the semiconductor chip 60 is placed so as to be covered with the adhesive surface of the adhesive layer (X2) of the adhesive sheet (II). A known device such as a flip chip bonder or a die bonder can be used for mounting the semiconductor chip.
The layout of the arrangement of the semiconductor chips 60, the number of arrangements, and the like may be appropriately determined according to the form of the target package, the number of production, and the like.

Here, as a manufacturing method of one aspect of the present invention, the semiconductor chip 60 is covered with a sealing material in a region larger than the chip size, as in FOWLP, FOPLP, etc., and not only the circuit surface of the semiconductor chip 60 but also the sealing material is sealed. It is preferable that it is applied to a package that forms a rewiring layer also in the surface region of the stop material.
Therefore, the semiconductor chip 60 is placed on a part of the adhesive surface of the pressure-sensitive adhesive layer (X2), and the adhesive surface is in a state where a plurality of semiconductor chips 60 are aligned at regular intervals. It is preferable that the plurality of semiconductor chips 60 are placed on the adhesive surface in a state of being arranged in a matrix of a plurality of rows and a plurality of columns at regular intervals.
The distance between the semiconductor chips 60 may be appropriately determined according to the form of the target package and the like.

Then, in the step (2-B), the semiconductor chip 60 and the adhesive surface of the pressure-sensitive adhesive layer (X1) at least in the peripheral portion of the semiconductor chip 60 are coated with a sealing material (hereinafter, "coating step"). The encapsulant is cured to obtain a cured encapsulant 61 in which the semiconductor chip 60 is sealed in the cured encapsulant (hereinafter, also referred to as “curing step”).
By placing the semiconductor chip 60 on a part of the adhesive surface of the pressure-sensitive adhesive layer (X2), a peripheral portion of the semiconductor chip 60 is formed in the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2).
That is, the peripheral portion of the semiconductor chip 60 refers to the adhesive surface of the pressure-sensitive adhesive layer (X2) corresponding to the gap between the adjacent semiconductor chips 60 among the plurality of semiconductor chips 60.

In the coating step of the step (2-B), first, the semiconductor chip 60 and the peripheral portion of the adhesive surface of the pressure-sensitive adhesive layer (X2) of the semiconductor chip 60 are coated with a sealing material. The encapsulant covers the entire exposed surface of the semiconductor chip CP and is also filled in the gaps between the plurality of semiconductor chip CPs.

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

As a method of coating the semiconductor chip 60 and its peripheral portion with a sealing material, an appropriate method is selected and applied according to the type of the sealing material from the methods conventionally applied to the semiconductor sealing step. For example, a roll laminating method, a vacuum pressing method, a vacuum laminating method, a spin coating method, a die coating method, a transfer molding method, a compression molding molding method, or the like can be applied.

Then, after performing the coating step, the sealing material is cured to obtain a cured sealing body 61 in which the semiconductor chip 60 is sealed by the cured sealing material.
The coating step and the curing step of the step (2-B) are preferably performed under temperature conditions lower than the expansion start temperature (t) of the heat-expandable particles.
Further, the coating step and the curing step may be carried out separately, but when the encapsulant is heated in the coating step, the encapsulant is cured as it is by the heating, and the coating step and the curing step are performed. May be carried out at the same time.
In the production example shown in FIG. 5, the step (4) is performed after the step (3), but after the step (2-B), one or more processes in the step (2). The step (4) may be carried out. In this case, the cured encapsulant can be subjected to the next step in a state of being attached to the adhesive sheet (II) without being separated from the adhesive sheet (II).
That is, in the manufacturing method of one aspect of the present invention, the object to be processed is a semiconductor chip, and one or more processes in the step (2) include the following steps (2-B).
Step (2-B): The semiconductor chip and the peripheral portion of the adhesive surface of the pressure-sensitive adhesive layer (X2) are covered with a sealing material, and the sealing material is cured. Step of obtaining a cured encapsulant obtained by encapsulating the semiconductor chip in a cured encapsulant Step (4) is carried out in at least one of the following (XB) and (YB).
(XB): Performed after the step (2-B) as the one or more processes (YB): Performed after the step (3)

<Process (3)>
In the step (3), the pressure-sensitive adhesive sheet (I) of the adhesive laminate and the base material (Y2) of the adhesive sheet (II) are subjected to heat treatment (heat treatment for separation) at a temperature equal to or higher than the expansion start temperature (t). Separate at the interface P with.
4 (c) and 5 (c) are schematic cross-sectional views showing a state of being separated at the interface P by the heat treatment for separation.
FIGS. 4 (c) and 5 (c) show a state in which the processed objects that have undergone the predetermined processing are separated on the adhesive sheet (II) by the separation heat treatment.

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

In this way, the adhesive sheet (II) is separated from the adhesive sheet (I) and separated from the support in a state where the objects to be processed that have been subjected to the predetermined processing in the step (2) are laminated (pasted). Therefore, the work of attaching the separated object to be processed to the adhesive sheet can be omitted and the process can be used in the next step.

<Process (4)>
In the step (4), at least one of cutting and grinding is performed on the surface of the object to be processed opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached.
For example, by cutting the object to be processed, the object to be processed can be divided into a desired size. Further, by performing grinding, the object to be processed can be adjusted to a desired thickness. It is also possible to perform both cutting and grinding, divide the object to be machined, and adjust the thickness.

Further, for example, as shown in FIG. 4D, the surface of the semiconductor wafer in which the modified region serving as the division starting point is formed by irradiation with laser light is ground on the side opposite to the surface to which the adhesive sheet (II) is attached. By doing so, the semiconductor wafer is made thin so that it can be easily cut, and then a gap 72 is generated with the modified region 71 as the division starting point by the processing pressure of a grinding wheel or the like, so that the semiconductor wafer is made into a predetermined size. It can be separated into a semiconductor chip.

Further, as shown in FIG. 5 (d), by cutting the cured encapsulant 61, an individualized product 61a of the cured encapsulant obtained by individualizing the cured encapsulant 61 in units of semiconductor chip CP can be obtained. Can be done. The cutting method for individualizing the cured sealant 61 is not particularly limited, and examples thereof include cutting means such as a dicing saw.
Further, although not shown, the cured sealant 61 may be ground for the purpose of exposing the circuit surface of the semiconductor chip.

It should be noted that there may be further other steps between steps (1) and (4), before step (1), and after step (4). For example, it may have a rewiring forming step and the like.

Further, as described above, the step (4) may be carried out as one or more of the processes in the step (2), or may be carried out after the step (3). Further, the step (4) may be carried out as one or more processes in the step (2) and may be carried out after the step (3).
For example, as one or more processes in the step (2), grinding is performed on the surface of the object to be processed opposite to the surface to which the adhesive layer (X2) is attached, and the surface is cut after the step (3). It is also possible to do.
Further, as one or more processes in the step (2), one direction of the surface opposite to the surface to be attached to the pressure-sensitive adhesive layer (X2) of the object to be processed (for example, in the XY plane of the object to be processed). Cutting only in the X-axis direction) to divide the work object into strips, and after step (3), cut only in another direction (for example, the Y-axis direction of the XY plane of the work object) to make a strip. The workpiece divided into shapes may be further divided into smaller parts (for example, in a square shape).

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

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

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

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

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

<Storage shear modulus G'of the first pressure-sensitive adhesive layer (X11), the second pressure-sensitive adhesive layer (X12), and the pressure-sensitive adhesive layer (X2)>
The formed first pressure-sensitive adhesive layer (X11), second pressure-sensitive adhesive layer (X12), and pressure-sensitive adhesive layer (X2) were cut into a circle with a diameter of 8 mm, and the release material was removed and overlapped to obtain a thickness. The test sample was 3 mm.
A torsional shearing method using a viscoelasticity measuring device (manufactured by Antonio Par, device name "MCR300") under the conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a temperature rise rate of 3 ° C./min, and a frequency of 1 Hz. Measured the storage shear viscoelasticity G'of the test sample at a predetermined temperature.

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

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

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

<Adhesive resin>
Acrylic copolymer (i): It has a structural unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio). Acrylic copolymer with Mw 600,000.
-Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid = 86.0 / 8.0 / 5.0 / 1. An acrylic copolymer of Mw 600,000 having a structural unit derived from a raw material monomer consisting of 0 (mass ratio).

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

<Thermal expandable particles>
-Thermal expandable particles (i): Nippon Philite Co., Ltd., product name "Expancel 031DU40", expansion start temperature (t) = 90 ° C., average particle size (D ₅₀ ) = 22 μm, 90% particle size (D ₉₀ ) = 30 μm.

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

[Example 1]
In the adhesive laminate 1d shown in FIG. 2B, a release material was further laminated on the second adhesive layer (X12) of the adhesive sheet (I) and the adhesive layer (X2) of the adhesive sheet (II). An adhesive laminate having a structure and provided with an intermediate layer (Z2) between the base material (Y2) of the adhesive sheet (II) and the adhesive layer (X2) was produced by the following procedure.

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

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

(1-3) Preparation of base material (Y1) (1-3-1) Preparation of composition (y1-1) Terminal isocyanate urethane prepolymer obtained by reacting ester-type diol with isophorone diisocyanate (IPDI) 2-Hydroxyethyl acrylate was reacted with the bifunctional acrylic urethane-based oligomer having a mass average molecular weight (Mw) of 5000.
Then, 40% by mass (solid content ratio) of the acrylic urethane-based oligomer synthesized above, 40% by mass (solid content ratio) of isobornyl acrylate (IBXA) as an energy ray-polymerizable monomer, and phenylhydroxypropyl acrylate (HPPA). ) 20 parts by mass (solid content ratio) is blended, and 2.0 parts by mass (solid) of the photopolymerization initiator (i) is further added to the total amount (100 parts by mass) of the acrylic urethane-based oligomer and the energy ray-polymerizable monomer. A phthalocyanine-based pigment (0.2 parts by mass (solid content ratio)) was blended as an additive to prepare an energy ray-curable composition.
Then, the heat-expandable particles (i) were blended with the energy ray-curable composition to prepare a solvent-free composition (y1-1) containing no solvent.
The content of the heat-expandable particles (i) was 20% by mass with respect to the total amount (100% by mass) of the composition (y1-1).

(1-3-2) Preparation of base material (Y1) Polyethylene terephthalate (PET) film with a thickness of 50 μm, which is a non-thermally expandable base material (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4300”, probe tack value The prepared composition (y1-1) was applied onto the surface of (0 mN / 5 mmφ) to form a coating film.
Then, using an ultraviolet irradiation device (manufactured by Eye Graphics, product name "ECS-401GX") and a high-pressure mercury lamp (manufactured by Eye Graphics, product name "H04-L41"), the illuminance is 160 mW / cm ² , and the light intensity is 500 mJ /. The ^{coating film was cured by irradiating with ultraviolet rays under the condition of cm 2} , and a heat-expandable substrate (Y-1) having a thickness of 50 μm was formed. The above-mentioned illuminance and light amount at the time of ultraviolet irradiation are values measured using an illuminance / light amount meter (manufactured by EIT, product name "UV Power Pack II").
Further, the PET film which is the above-mentioned non-thermally expandable base material corresponds to the non-heat-expandable base material layer (Y1-2).
As a sample for measuring the physical property value of the heat-expandable base material layer (Y1-1), the resin composition is applied to the surface of the release agent layer of the light release film to form a coating film, and the coating is applied. The film was dried at 100 ° C. for 120 seconds to form a heat-expandable substrate layer (Y1-1) having a thickness of 50 μm in the same manner.
Then, based on the above-mentioned measuring method, the storage elastic modulus and the probe tack value at each temperature of the heat-expandable base material layer (Y1-1) were measured. The measurement results were as follows.
-Storage modulus at 23 ° C. E'(23) = 5.0 × 10 ⁸ Pa
Storage elastic modulus at 100 ° C. E'(100) = 4.0 × 10 ⁶ Pa
-Storage modulus at 208 ° C. E'(208) = 4.0 × 10 ⁵ Pa
・ Probe tack value = 2mN / 5mmφ

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

[2] Preparation of adhesive sheet (II) (2-1) Formation of adhesive layer (X2) The isocyanate-based cross-linking is applied to 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin. Agent (i) 8 parts by mass (solid content ratio) was blended, diluted with toluene, and uniformly stirred to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass.
Then, the pressure-sensitive adhesive composition is applied to the surface of the release agent layer of the heavy-release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to obtain a pressure-sensitive adhesive layer having a thickness of 20 μm. X2) was formed.
The adhesive strength of the pressure-sensitive adhesive layer (X2) measured based on the above method was 0.5 N / 25 mm.

(2-2) Base material (Y2)
The base material (Y2) was a polyethylene terephthalate (PET) film having a thickness of 50 μm (manufactured by Toyo Boseki Co., Ltd., product name “Cosmo Shine A4300”, probe tack value: 0 mN / 5 mmφ).

(2-3) Intermediate layer (Z2)
(1) Preparation of composition for forming intermediate layer 100 parts by mass of non-energy ray-curable acrylic copolymer C1, 68 parts by mass of energy ray-curable acrylic copolymer D1, tolylene diisocyanate-based cross-linking agent (commodity) Name: BHS 8515, manufactured by Toyochem Co., Ltd.) was added in an amount of 2.8 parts by mass, and the above-mentioned photopolymerization initiator (i) was added in an amount of 2.7 parts by mass, diluted with ethyl acetate, and solid content concentration (active ingredient concentration). A 35% by mass solution of the composition for forming an intermediate layer was prepared.

(2) Preparation of non-energy ray-curable acrylic copolymer C1 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AAc) are added to an ethyl acetate solvent, and azo is used as a polymerization initiator. 1.0 part by mass of bisisobutyronitrile (AIBN) was added and solution polymerization was allowed to proceed to obtain a non-energy ray-curable acrylic copolymer C1 (Mw: 500,000).

(3) Preparation of Energy Ray Curable Acrylic Copolymer D1 62 parts by mass of butyl acrylate (BA), 10 parts by mass of methyl methacrylate (MMA), and 28 parts by mass of 2-hydroxyethyl acrylate (HEA) are used in an ethyl acetate solvent. Azobisisobutyronitrile (AIBN) was added in an amount of 1.0 part by mass as a polymerization initiator to allow solution polymerization to proceed, and after a certain period of time, an acrylic copolymer (BA / MMA /) was added. HEA = 62/10/28 (mass%)) was obtained.
Subsequently, methacryloyloxyethyl isocyanate is added to the acrylic copolymer in an amount such that the number of isocyanate groups is 80 equivalents with respect to 100 equivalents of the total number of hydroxyl groups in the added HEA, and the reaction is carried out. An energy ray-curable acrylic copolymer D1 (Mw: 100,000) having a group was obtained. The value of β calculated from the above formula (2) in the energy ray-curable acrylic copolymer D1 is 22.4.

(4) Preparation of Intermediate Layer (Z2) On the peeled surface of the peeling sheet (manufactured by Lintec Corporation, trade name "SP-PET38131", polyethylene terephthalate film subjected to silicone peeling treatment, thickness: 38 μm). The solution of the intermediate layer forming composition prepared as described above was applied so as to have a thickness of 45 μm after drying to form a coating film. Next, the coating film was dried at 100 ° C. for 2 minutes to form an intermediate layer (Z2) to prepare a release sheet with an intermediate layer.
As for the release sheet with an intermediate layer, two identical sheets are prepared, and the intermediate layers of the two release sheets with an intermediate layer are bonded to each other, and two intermediate layers (Z2) having a thickness of 90 μm are peeled off. A laminated sheet sandwiched between sheets was obtained.

(2-4) Lamination of Each Layer An intermediate layer (Z2) having a thickness of 90 μm is sandwiched between two release sheets. One release sheet of the laminated sheet is removed, and the exposed intermediate layer (Z2) is on the surface. The base material (Y2) was laminated on the surface.
Further, the other release sheet is also removed, and the adhesive layer (X2) formed in the above (2-1) is adhered on the surface of the exposed intermediate layer (Z2) to form a base material (Y2) / intermediate layer. An adhesive sheet (II) was prepared by laminating (Z2) / adhesive layer (X2) / heavy release film in this order.

[3] Preparation of Adhesive Laminated Body The first pressure-sensitive adhesive layer (X11) exposed by removing the heavy-release film of the pressure-sensitive adhesive sheet (I) prepared in the above [1] and the base material of the pressure-sensitive adhesive sheet (II). (Y2) was bonded to obtain an adhesive laminate.

The adhesive laminate is separated at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) before and after the heat treatment. The peeling force (F ₀ ) and (F ₁ ) at the time were measured based on the following method.
As a result, the peeling force (F ₀ ) = 0.5 N / 25 mm and the peeling force (F ₁ ) = 0 mN / 25 mm, and the ratio of _{the peeling force (F 1} ) to the peeling force (F _{0 ) [(F 1} ) / (F ₀ )] was 0.

<Measurement of peeling force (F _0)>
The prepared adhesive laminate was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and then the heavy release film contained in the adhesive sheet (II) of the adhesive laminate was removed and exposed. The adhesive layer (X2) was attached to a stainless steel plate (SUS304, 360 polishing).
Next, the end of the stainless steel plate to which the adhesive laminate was attached was fixed to the lower chuck of a universal tensile tester (manufactured by Orientec, product name "Tencilon UTM-4-100").
Further, the upper chuck of the universal tensile tester is peeled off at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the base material (Y2) of the pressure-sensitive adhesive sheet (II). The adhesive sheet (I) of the adhesive laminate was fixed with.
Then, under the same environment as above, the peeling force measured when peeling at the interface P at a tensile speed of 300 mm / min by the 180 ° peeling method based on JIS Z0237: 2000 is referred to as "peeling force (F ₀ )". ".

<Measurement of peeling force (F _1)>
The heavy-release film contained in the pressure-sensitive adhesive sheet (II) of the produced pressure-sensitive adhesive laminate was removed, and the exposed pressure-sensitive adhesive layer (X2) was attached to a stainless steel plate (SUS304, No. 360 polishing).
Then, the stainless steel plate and the adhesive laminate were heated at 240 ° C. for 3 minutes to expand the thermally expandable particles in the thermally expandable base material layer (Y1-2) of the adhesive laminate.
After that, in the same _{manner as the above-mentioned measurement of the peeling force (F 0} ), under the above conditions, the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are combined. The peeling force measured when peeling at the interface P was defined as "peeling force (F ₁ )".
In the measurement of the peeling force (F ₁ ), when the adhesive sheet (I) of the adhesive laminate was to be fixed by the upper chuck of the universal tensile tester, the adhesive sheet (I) was completely separated at the interface P. If it could not be fixed, the measurement was terminated and the peeling force (F ₁ ) at that time was set to "0 mN / 25 mm".

[Example 2]
An adhesive sheet (II) to which the object to be processed was attached was prepared by the following procedure.
(1) Fixing the semiconductor wafer The light release film of the adhesive laminate produced in Example 1 is removed, and the adhesive surface of the second adhesive layer (X12) of the exposed adhesive sheet (I) is supported (1). Glass) and pasted.
Then, the surface of the semiconductor wafer having the circuit surface on which the pattern is formed on the circuit surface side and the adhesive layer (X2) of the adhesive sheet (II) are bonded to each other, and the adhesive laminate produced in Example 1 is used. A semiconductor wafer was fixed to the support.

(2) Formation of modified region Using a stealth laser irradiation device (manufactured by Tokyo Seimitsu Co., Ltd., device name "ML300PlusWH"), stealth laser irradiation is performed from the surface opposite to the circuit forming surface of the semiconductor wafer to perform stealth laser irradiation. A modified region serving as a division starting point was formed inside.

(3) Separation at Interface P After the above (2), the adhesive laminate was heat-treated at 120 ° C., which is equal to or higher than the expansion start temperature (90 ° C.) of the heat-expandable particles, for 3 minutes. Then, at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II), it was possible to easily separate them all at once.
Then, after separation, a pressure-sensitive adhesive sheet (II) in which a semiconductor wafer having a modified region formed therein was attached was obtained.

1a, 1b, 1c, 1d, 2 Adhesive laminate (I) Adhesive sheet (X1) Adhesive layer (X11) First adhesive layer (X12) Second adhesive layer (Y1) Base material (Y1-1) Thermally expandable base material layer (Y1-2) Non-heat expandable base material layer (II) Adhesive sheet (X2) Adhesive layer (Z2) Intermediate layer (Y2) Base material 50 Supports 60, 70 Processed object 61 Hardened Encapsulant 61a Individual fragment of cured encapsulant 71 Modified region 72 Gap

Claims (17)

A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and an adhesive layer (X1) and containing heat-expandable particles having a thermal expansion start temperature (t) in any of the layers, and a base material ( Using an adhesive laminate having an adhesive sheet (II) having Y2) and an adhesive layer (X2) and directly laminating the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). , A method of manufacturing a processed product that has been subjected to at least one of cutting and grinding.
The following steps (1) to (3) are performed in this order.
Step (1): A step of attaching the surface of the pressure-sensitive adhesive layer (X1) of the adhesive laminate to the support and attaching the object to be processed to the surface of the pressure-sensitive adhesive layer (X2) of the adhesive laminate. -Step (2): A step of performing one or more processing on the processing object-Step (3): By heating the heat-expandable particles at a thermal expansion start temperature (t) or higher, the processing object is adhered to the adhesive. The adhesive laminate is separated at the interface P between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) while maintaining the state of being attached to the surface of the adhesive layer (X2) of the adhesive laminate. Steps to be performed Further, it has the following step (4).
Step (4): A step of performing at least one of cutting and grinding on the surface of the object to be processed opposite to the surface to which the adhesive layer (X2) is attached. The step (4) is as follows. A method for producing a processed product, which is carried out in at least one of (X) and (Y).
(X): Performed in the step (2) as the one or more processes (Y): Performed after the step (3) The production method according to claim 1, wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270 ° C. The production method according to claim 1 or 2, wherein the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) containing the heat-expandable particles. The production method according to claim 3, wherein the base material (Y1) contained in the pressure-sensitive adhesive sheet (I) has a heat-expandable base material layer (Y1-1) and a non-heat-expandable base material layer (Y1-2). .. Claim 3 or 4 in which the heat-expandable base material layer (Y1-1) of the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. The manufacturing method described in. The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is sandwiched between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12).
It has a structure in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
The manufacturing method according to any one of claims 3 to 5, wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support. The first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles.
The second pressure-sensitive adhesive layer (X12) is a non-thermally expandable pressure-sensitive adhesive layer.
The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
The manufacturing method according to claim 1 or 2, wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support. The production method according to claim 6 or 7, wherein the surface on the side where the first pressure-sensitive adhesive layer (X11) of the base material (Y1) is laminated is the surface to which the easy-adhesion treatment is applied. The production method according to any one of claims 1 to 8, wherein the surface on the side where the pressure-sensitive adhesive sheet (I) of the base material (Y2) is laminated is the surface to which the peeling treatment has been performed. The production method according to any one of claims 1 to 9, wherein the pressure-sensitive adhesive sheet (II) has an intermediate layer (Z2) between the base material (Y2) and the pressure-sensitive adhesive layer (X2). The production method according to any one of claims 1 to 10, wherein the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is an energy ray-curable pressure-sensitive adhesive layer. The production method according to any one of claims 1 to 11, wherein the adhesive sheet (II) satisfies one or more of the following requirements (α) to (γ).
-Requirement (α): Young's modulus of the base material (Y2) is 1.0 MPa or more.
-Requirement (β): The thickness of the base material (Y2) is 5 μm or more.
-Requirement (γ): The storage elastic modulus G'(23 ° C.) of the pressure-sensitive adhesive layer (X2) is 0.1 MPa or more. The object to be processed is a semiconductor wafer.
The one or more processes in the step (2) include the following steps (2-A).
Step (2-A): A step of forming a modified region serving as a division starting point on the semiconductor wafer. The step (4) is the following step (4-A).
Step (4-A): A step of grinding the surface of the semiconductor wafer opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached. ) Or (YA), the manufacturing method according to any one of claims 1 to 12.
(XA): Performed after the step (2-A) as the one or more processes (YA): Performed after the step (3) The object to be processed is a semiconductor chip,
The one or more processes in the step (2) include the following steps (2-B).
Step (2-B): The semiconductor chip and the peripheral portion of the adhesive surface of the pressure-sensitive adhesive layer (X2) are covered with a sealing material, and the sealing material is cured. Step of obtaining a cured encapsulant obtained by encapsulating the semiconductor chip in a cured encapsulant The step (4) is carried out in at least one of the following (XB) and (YB). Item 2. The production method according to any one of Items 1 to 12.
(XB): Performed after the step (2-B) as the one or more processes (YB): Performed after the step (3) A semiconductor wafer in which the object to be processed has a modified region as a starting point for division.
The production method according to any one of claims 1 to 12, wherein the step (4) is the following step (4-A).
Step (4-A): A step of grinding the surface of the semiconductor wafer on the side opposite to the surface to which the pressure-sensitive adhesive layer (X2) is attached. A semiconductor wafer in which the object to be processed has a notch groove as a division starting point.
The production method according to any one of claims 1 to 12, wherein the step (1) is the following step (1-C), and the step (4) is the following step (4-C).
Step (1-C): The surface of the adhesive layer (X1) of the adhesive laminate is attached to the support, and the semiconductor wafer is cut into the surface of the adhesive layer (X2) of the adhesive laminate. Step / Step (4-C) of attaching the grooved surface: A step of grinding the surface of the semiconductor wafer opposite to the surface to which the adhesive layer (X2) is attached. A heat-expandable pressure-sensitive adhesive sheet (I) having a base material (Y1) and a pressure-sensitive adhesive layer (X1) and containing heat-expandable particles in any of the layers, and a base material (Y2) and a pressure-sensitive adhesive layer (X2). ) Is provided, and the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated, and is processed by at least one of cutting and grinding. Adhesive laminate for manufacturing products.

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