WO2019112033A1

WO2019112033A1 - Adhesive laminate, usage method of adhesive laminate, and manufacturing method for semiconductor device

Info

Publication number: WO2019112033A1
Application number: PCT/JP2018/045056
Authority: WO
Inventors: 中山　武人; 岡本　直也; 高志阿久津
Original assignee: リンテック株式会社
Priority date: 2017-12-07
Filing date: 2018-12-07
Publication date: 2019-06-13
Also published as: TWI785161B; CN112203840A; CN112203840B; JP7405618B2; KR102609670B1; TW201930515A; KR20200092318A; JPWO2019112033A1

Abstract

This adhesive laminate is provided with: a thermally-expandable adhesive sheet (I) which has a substrate (Y1) and an adhesive-agent layer (X1) and in which any one layer contains thermally expandable particles having an expansion initiation temperature (t) of 60-270°C; and an adhesive sheet (II) which has a substrate (Y2) and an adhesive-agent layer (X2) disposed on one surface side of the substrate (Y2), the adhesive laminate being formed by directly layering the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), wherein separation takes place at an interface P between the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) by a heating treatment applied at a temperature that is equal to or greater than the expansion initiation temperature (t).

Description

Adhesive laminate, method of using adhesive laminate, and method of manufacturing semiconductor device

The present invention relates to an adhesive laminate, a method of using the adhesive laminate, and a method of manufacturing a semiconductor device using the adhesive laminate.

The adhesive sheet is used not only for semi-permanently fixing members but also for temporarily fixing members for temporarily fixing target members when processing or inspecting construction materials, interior materials, electronic parts, etc. There is a case.
Such an adhesive sheet for temporary fixing use is required to have both adhesiveness during use and releasability after use.

For example, Patent Document 1 discloses a heat-peelable 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 side of a substrate. There is.
This heat-peelable 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 the centerline average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating It is adjusted to 0.4 μm or less.
In Patent Document 1, the heat-peelable pressure-sensitive adhesive sheet can ensure a contact area with an adherend at the time of cutting an electronic component, and can therefore exhibit adhesiveness capable of preventing adhesion failure such as chip fly, etc. After use, there is a description that it can be easily peeled off by heating to expand the thermally expandable microspheres and reducing the contact area with the adherend.

Patent No. 3594853 gazette

In the processing or inspection step using the temporary fixing adhesive sheet as described in Patent Document 1, the target object is temporarily fixed using the temporary fixing adhesive sheet, and after the processing or inspection is performed, the target object is In general, it is separated from the temporary fixing adhesive sheet and taken out.
By the way, especially in the manufacture of electronic components, there are many cases in which a plurality of processing steps and inspection steps are performed.
Therefore, the target after processing or inspection has already been separated from the temporary fixing adhesive sheet, so when it is necessary to attach the adhesive sheet in the next step, another new temporary fixing adhesive sheet The process of the next step is performed after the

However, for example, there are cases where the object after processing is finely cut and it is difficult to apply the pressure-sensitive adhesive sheet as compared to before processing. In addition, the work of attaching a new adhesive sheet in each process affects the productivity of the product.
In addition, in the case where the object is thinned and fragile, the handling property may be lacking, which may cause an adverse effect such as difficulty in transportation to the next process.
Furthermore, in the case of an object having a circuit surface, it is necessary to protect the circuit surface in order to suppress the contamination of the circuit surface.

According to the present invention, a processing inspection object can be fixed to a support and predetermined processing and / or inspection can be performed, and after processing and / or inspection, the processing inspection object from the support with a slight force An object of the present invention is to easily manufacture a processing inspection object with a pressure sensitive adhesive sheet having a protective function and a supporting performance with respect to a processing inspection object after being easily separated at once and separated from a support. It is an object of the present invention to provide an adhesive laminate capable of

The present inventors have a substrate and a pressure-sensitive adhesive layer, and a thermally expandable pressure-sensitive adhesive sheet (I) having a layer containing thermally expandable particles, and a pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer (II) And a pressure-sensitive adhesive sheet (I) and a substrate of the pressure-sensitive adhesive sheet (II) are directly laminated to each other.

That is, the present invention relates to the following [1] to [19].
[1] A thermally expandable pressure-sensitive adhesive sheet comprising thermally expandable particles having a substrate (Y1) and an adhesive layer (X1) and having an expansion start temperature (t) of 60 to 270 ° C. in any layer ((1) I) and
And a pressure-sensitive adhesive sheet (II) having a substrate (Y2) and a pressure-sensitive adhesive layer (X2) on one surface side of the substrate (Y2),
A pressure-sensitive adhesive laminate (I) and a substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
The adhesive laminated body isolate | separated in the interface P of adhesive sheet (I) and the base material (Y2) of adhesive sheet (II) by heat processing at temperature more than expansion | swelling start temperature (t).
[2] The pressure-sensitive adhesive laminate according to the above [1], which has a peeling force (F ₁ ) of 0 to 2000 mN / 25 mm when separated at the interface P by the heat treatment.
[3] The peeling force (F ₀ ) at the time of separation at the interface P before performing the heat treatment is 100 mN / 25 mm or more and larger than the peeling force (F ₁ ), the above [1] or [2] The adhesive laminate as described in.
[4] The pressure-sensitive adhesive laminate according to the above-mentioned [3], wherein the ratio [(F ₁ ) / (F ₀ )] between the peeling force (F ₁ ) and the peeling force (F ₀ ) is 0 to 0.9. .
[5] The pressure-sensitive adhesive laminate according to any one of the above [1] to [4], wherein the probe tack value on the surface of the substrate (Y1) is less than 50 mN / 5 mmφ.
[6] Any one of the above-mentioned [1] to [5], wherein the substrate (Y1) of the pressure-sensitive adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing the thermally expandable particles. The adhesive laminate as described in 1).
[7] The heat expandable substrate layer (Y1-1) of the substrate (Y1) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated The adhesive laminated body as described in [6].
[8] The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is held between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12),
The pressure-sensitive adhesive laminate according to the above [6] or [7], having a configuration in which the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. body.
[9] The adhesive laminate according to the above [8], wherein the adhesive force of the second adhesive layer (X12) is higher than the adhesive force of the first adhesive layer (X11).
[10] The substrate (Y1) has a thermally expandable substrate layer (Y1-1) on one surface side and a non-thermally expandable substrate layer (Y1-2) on the other surface side, The adhesive laminate according to any one of the above [6] to [9].
[11] The first pressure-sensitive adhesive layer (X11) is laminated on the surface side of the thermally expandable base material layer (Y1-1),
The second pressure-sensitive adhesive layer (X12) is laminated on the surface side of the non-thermally expandable substrate layer (Y1-2),
The adhesive laminated body as described in said [10].
[12] A first pressure-sensitive adhesive layer (X11), which is a thermally expandable pressure-sensitive adhesive layer containing thermally expandable particles on both sides of the substrate (Y1), respectively, and a non-thermally expandable adhesive A second pressure-sensitive adhesive layer (X12) which is an adhesive layer,
The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated,
The adhesive laminate according to any one of the above [1] to [5].
[13] The pressure-sensitive adhesive laminate according to the above [12], wherein the content of the thermally expandable particles in the second pressure-sensitive adhesive layer (X12) which is a non-thermally expandable pressure-sensitive adhesive layer is less than 1% by mass.
[14] A use method of the pressure-sensitive adhesive laminate having the following steps (1) to (3).
Step (1): A processing and inspection object is fixed to a support via the adhesive laminate according to any one of the above [1] to [13], and the support, the adhesive laminate And laminating the processing inspection object in this order.
Step (2): a step of processing and / or inspecting the object to be processed and inspected.
Step (3): Separation at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) Process.
[15] A step (1) adheres the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate and the support, and the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate The usage method of the adhesive laminated body as described in said [14] which is a process of sticking an adhesive layer (X1) and the said processing inspection target object.
[16] A step (1) adheres the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the support, and the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate The usage method of the adhesive laminated body as described in said [14] which is a process of sticking an adhesive layer (X2) and the said processing inspection target object.
[17] A method of manufacturing a semiconductor device using the adhesive laminate according to any one of the above [1] to [13], which has the following steps (i) to (iii): Manufacturing method.
Step (i): The pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the pressure-sensitive adhesive surface (X2) of the pressure-sensitive adhesive sheet (II) And attaching the semiconductor chip to a part of the other adhesive surface.
Step (ii): covering the semiconductor chip and the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2) of at least the periphery of the semiconductor chip with a sealing material, and curing the sealing material, A step of obtaining a cured sealing body in which the semiconductor chip is sealed in a curing sealing material.
Step (iii): Separation at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) And a step of obtaining a cured seal with a pressure-sensitive adhesive sheet, wherein the cured seal is laminated on the pressure-sensitive adhesive sheet (I) or (II).
[18] In the step (i), adhere the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) to the support, and part of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) The method for manufacturing a semiconductor device according to the above [17], wherein the semiconductor chip is mounted.
[19] In the step (i), the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the support are attached, and part of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) The method for manufacturing a semiconductor device according to the above [17], wherein the semiconductor chip is mounted.

The adhesive laminate of the present invention is capable of fixing a processing inspection object to a support to carry out predetermined processing and / or inspection and subjecting processing inspection with a slight force after the processing and / or inspection. The object to be processed can be easily separated at once from the support together with the adhesive sheet having a protective function and a supporting ability for the object to be processed after being separated from the support. can do.

It is a cross-sectional schematic diagram of the said adhesive laminated body which shows the structure of the adhesive laminated body of a 1st aspect of this invention. It is a cross-sectional schematic diagram of the said adhesive laminated body which shows the structure of the adhesive laminated body of the 2nd aspect of this invention. It is a cross-sectional schematic diagram of the said adhesive laminated body which shows the structure of the adhesive laminated body of 3rd aspect of this invention. (A) is a cross-sectional schematic diagram which shows an example of the state which fixed the process test object to the support body via the adhesive laminated body of this invention, (b) is separated in the interface P by heat processing. It is a cross-sectional schematic diagram which shows the state which was carried out. (A) is a cross-sectional schematic diagram which shows another example of the state which fixed the process inspection target object to the support body via the adhesive laminated body of this invention, (b) is the interface P by heat processing. It is a cross-sectional schematic diagram which shows the state isolate | separated by.

In the present specification, the determination as to whether or not the layer is a "non-thermally expandable layer" is based on the expansion start temperature (t) of the thermally expandable particles contained in the layer containing thermally expandable particles. When the heat treatment for 3 minutes is performed, if the volume change rate calculated from the following equation is less than 5%, the layer is determined to be a "non-thermally expandable layer".
Volume change rate (%) = (volume of the layer after heat treatment−volume of the layer before heat treatment) / volume of the layer before heat treatment × 100

In the present specification, the "active ingredient" refers to the ingredient contained in the composition of interest excluding the diluent solvent.
Moreover, mass mean molecular weight (Mw) is a value of standard polystyrene conversion measured by gel permeation chromatography (GPC) method, and is specifically a value measured based on the method as described in an Example.

In the present specification, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the other similar terms are also the same.
Moreover, the lower limit and upper limit which were described in steps can be combined independently, respectively about a preferable numerical range (for example, ranges, such as content etc.). For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferred lower limit (10)” and “more preferred upper limit (60)” are combined to obtain “10 to 60”. It can also be done.

[Composition of adhesive laminate]
The adhesive laminate of the present invention has a substrate (Y1) and an adhesive layer (X1), and includes thermally expandable particles having an expansion start temperature (t) of 60 to 270 ° C. in any layer. A pressure-sensitive adhesive sheet comprising: an expandable pressure-sensitive adhesive sheet (I), a substrate (Y2), and a pressure-sensitive adhesive sheet (II) having a pressure-sensitive adhesive layer (X2) on one surface side of the substrate (Y2) It forms by laminating | stacking (I) and the base material (Y2) of adhesive sheet (II) directly.
Then, the adhesive laminate of the present invention is separated at the interface P between the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) be able to.
FIGS. 1 to 3 are cross-sectional schematic views of the pressure-sensitive adhesive laminate showing the constitution of the pressure-sensitive adhesive laminate of the first to third embodiments of the present invention.

As an adhesive laminated body of 1 aspect of this invention, adhesive laminated body 1a, 1b shown to FIG. 1 (a), (b) is mentioned, for example.
The adhesive laminates 1a and 1b are a pressure-sensitive adhesive sheet (I) having a substrate (Y1) and a pressure-sensitive adhesive layer (X1), and a pressure-sensitive adhesive sheet (II) having a substrate (Y2) and a pressure-sensitive adhesive layer (X2) And 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 pressure-sensitive adhesive laminate of the present invention, any layer of the pressure-sensitive adhesive sheet (I) has a thermal expansion start temperature (t) of 60 to 270 ° C. so that separation can be performed at the interface P by the heat treatment. It is a layer containing expandable particles.
In the pressure-sensitive adhesive laminate of the present invention, the heat-expandable particles are expanded by heat treatment at a temperature higher than the expansion start temperature (t), and unevenness is generated on the surface of the layer containing the heat-expandable particles. The contact area of the sheet (II) with the substrate (Y2) can be reduced.
As a result, for example, the processing inspection object is placed on the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) or the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II), and subjected to processing and / or inspection. Then, they are separated at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) to obtain a processing inspection object attached to the pressure-sensitive adhesive sheet (I) or (II) .

Therefore, the adhesive laminate of the present invention can fix a processing inspection object to a support and carry out predetermined processing and / or inspection, and process with a slight force after the processing and / or inspection. The object to be inspected can be easily separated at one time from the support, and after being separated from the support, the object to be processed and inspected is an adhesive sheet provided with a protective function and a supporting performance for the object to be processed and inspected It can be a thing.
In the following description, "processing inspection object" may be simply expressed as "object".
Using the adhesive laminate of the present invention has, for example, the following advantages.
-In the next step, there is no need to perform an operation of newly sticking an adhesive sheet on the processing and inspection object after separation.
-Even when the target is thin and fragile, the adhesive sheet is attached to the target, so that the support performance is given, and the handleability such as transportation to the next step can be made favorable.
-In the case of an object having a circuit surface, the circuit surface can be protected by attaching an adhesive sheet to the circuit surface of the object.

In one aspect of the present invention, as in the adhesive laminates 1a and 1b shown in FIG. 1, the substrate (Y1) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles. Is preferred.
In addition, as such a base material (Y1), it comprises only from the thermally expandable base material layer (Y1-1) containing the said thermally expandable particle like the adhesive laminated body 1a shown to Fig.1 (a). The heat-expandable base material layer (Y1-1) and the non-heat-expandable base material layer (Y1-2) as shown in FIG. 1 (b) may be used. And may have a multi-layered structure.

The adhesive laminate 1a shown in FIG. 1 (a) is a substrate (Y2) of the pressure-sensitive adhesive sheet (I) of the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) by the heat treatment. Irregularities occur on the side surface, and the contact area of the pressure-sensitive adhesive sheet (II) with the substrate (Y2) decreases.
As a result, the adhesive laminate 1a can be easily separated in a single operation with a slight force at the interface P between the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) It becomes.

In one aspect of the present invention, the thermally expandable base material layer of the base material (Y1) that the adhesive sheet (I) has, from the viewpoint of forming an adhesive laminate that can be easily separated at one time with a slight force at interface P. It is preferable that (Y1-1) and the base material (Y2) of the pressure-sensitive adhesive sheet (II) be directly laminated.

Moreover, in the case of the aspect whose base material (Y1) is a multilayer structure like the adhesive laminated body 1b shown in FIG.1 (b), the heat expansion base material layer of a base material (Y1) by the said heat processing The thermally expandable particles contained in (Y1-1) expand to produce asperities on the surface of the thermally expandable substrate layer (Y1-1) on the side of the substrate (Y2).
On the other hand, the non-thermally expandable substrate layer (Y1-2) of the substrate (Y1) has a small degree of expansion due to the heat treatment, so the pressure-sensitive adhesive of the non-thermally expandable substrate layer (Y1-2) Irregularities are less likely to be formed on the surface on which the layer (X1) is laminated.
As a result, the pressure-sensitive adhesive laminate 1b is batched with a slight force at the interface P between the base (Y1) of the pressure-sensitive adhesive sheet (I) and the base (Y2) of the pressure-sensitive adhesive sheet (II) by the heat treatment. While being easily separable, the adhesion between the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the adherend to be attached can be well maintained even after the heat treatment.

From the above viewpoint, in one aspect of the present invention, as in the case of the adhesive laminate 1b shown in FIG. 1 (b), the base (Y1) is a heat expandable base layer (Y1-1) on one surface side. It is preferable to have the non-heat-expandable substrate layer (Y1-2) on the other surface side.

In the adhesive laminate of one embodiment of the present invention, as in the adhesive laminates 1c and 1d shown in FIG. 2, the adhesive sheet (I) comprises the first adhesive layer (X11) and the second adhesive layer. The substrate (Y1) is sandwiched by (X12), and the first pressure-sensitive adhesive layer (X11) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated. It is also good.

For example, in the adhesive laminate 1c shown in FIG. 2A, the thermally expandable particles in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) are expanded by the heat treatment. The unevenness occurs on the surface on the side of the first pressure-sensitive adhesive layer (X11). The first pressure-sensitive adhesive layer (X11) is also pushed up by the unevenness generated on the surface of the thermally expandable base material layer (Y1-1), and the unevenness is also formed on the surface of the first pressure-sensitive adhesive layer (X11). The contact area of the (II) with the substrate (Y2) is reduced.
As a result, it becomes possible to separate easily collectively with a slight force at the interface P between the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II).

In the case of the configuration as the adhesive laminate 1c of FIG. 2 (a), the expansion of the thermally expandable particles in the thermally expandable base material layer (Y1-1) makes it possible to obtain the first adhesive layer (X11). Not only the surface but also the surface of the second pressure-sensitive adhesive layer (X12) may have irregularities.
In particular, when the processing and inspection object is placed on the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I), adhesion to the processing and inspection object and adhesion in the next step after separation at the interface P Adhesion to the sheet (I) is often required.
Therefore, in the pressure-sensitive adhesive laminate of one aspect of the present invention, the adhesion of the second pressure-sensitive adhesive layer (X12) is preferably higher than the adhesion of the first pressure-sensitive adhesive layer (X11).
The adhesive strength of the pressure-sensitive adhesive layer is, for example, the kind and amount of the adhesive resin, tackifier, crosslinking agent, catalyst, etc. contained in the pressure-sensitive adhesive composition which is a forming material of the pressure-sensitive adhesive layer It is possible to adjust by setting the thickness.

Moreover, in the adhesive laminate of one embodiment of the present invention, as in the adhesive laminate 1 d shown in FIG. 2 (b), the base (Y 1) of the adhesive sheet (I) is a thermally expandable base layer ( A first pressure-sensitive adhesive layer (X11) is laminated on the surface side of the thermally expandable base material layer (Y1-1) having Y1-1) and a non-thermally expandable base material layer (Y1-2). It is preferable to have a configuration in which the second pressure-sensitive adhesive layer (X12) is laminated on the surface side of the thermally expandable base material layer (Y1-2).
If it is a configuration as in the adhesive laminate 1d of FIG. 2 (b), the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) of the substrate (Y1) are expanded by the heat treatment. As a result, the surface of the thermally expandable base material layer (Y1-1) has irregularities, and the surface of the first pressure-sensitive adhesive layer (X11) also has irregularities. As a result, the contact area between the first pressure-sensitive adhesive layer (X11) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) is reduced.
On the other hand, the formation of irregularities on the surface on the second pressure-sensitive adhesive layer (X12) side of the thermally expandable substrate layer (Y1-1) is suppressed by the presence of the non-thermally expandable substrate layer (Y1-2) There is. Therefore, the formation of unevenness is suppressed on the surface of the second pressure-sensitive adhesive layer (X12), the contact area with the adherend is sufficiently ensured, and good adhesion with the adherend is maintained. it can.

The

adhesive laminates

1a, 1b, 1c and 1d shown in FIGS. 1 and 2 each include a layer containing the thermally expandable particles as one of the layers constituting the substrate (Y1). It is.
On the other hand, as another aspect of the adhesive laminate of the present invention, a thermally expandable adhesive layer containing the thermally expandable particles is provided on the surface on the interface P side of the substrate (Y1) of the adhesive sheet (I) The non-heat-expandable pressure-sensitive adhesive layer may be provided on the surface of the other side of the base (Y1).
As the adhesive laminate of such an embodiment, specifically, like the adhesive laminate 2 shown in FIG. 3, the adhesive sheet (I) is thermally expanded on both sides of the substrate (Y1). Of a first pressure-sensitive adhesive layer (X11) which is a heat-expandable pressure-sensitive adhesive layer containing particulates and a second pressure-sensitive adhesive layer (X12) which is a non-heat-expandable pressure-sensitive adhesive layer The adhesive laminated body formed by laminating | stacking the 1 adhesive layer (X11) and the base material (Y2) of 2nd adhesive sheet (II) directly is preferable.
In the adhesive laminate, the substrate (Y1) is preferably a non-thermally expandable substrate.

In the adhesive laminate 2 shown in FIG. 3, as a result of the heat treatment, unevenness occurs on the surface of the thermally expandable pressure-sensitive adhesive layer which is the first pressure-sensitive adhesive layer (X11), and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) The contact area with) decreases.
As a result, the pressure-sensitive adhesive laminate 2 is easily collectively at a slight force 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). Can be separated.

On the other hand, the surface on the substrate (Y1) side of the first pressure-sensitive adhesive layer (X11) is also uneven due to the heat treatment by laminating the substrate (Y1) which is a non-thermal expansion substrate. It becomes difficult.
In addition, since the second pressure-sensitive adhesive layer (X12) is a non-heat-expandable pressure-sensitive adhesive layer, the adhesion to the adherend adhered to the second pressure-sensitive adhesive layer (X12) is good even by the heat treatment. Can be maintained.

In the pressure-sensitive adhesive laminate of one embodiment 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 adherend.
Also, for example, in the adhesive laminate 1a shown in FIG. 1 (a), one in which the release material subjected to release treatment on both sides is laminated on one adhesive surface of the pressure-sensitive adhesive layers (X1) and (X2) , May be wound in a roll. About the adhesive laminate 1b shown in FIG. 1 (b), the adhesive laminate 1c shown in FIG. 2 (a), the adhesive laminate 1d shown in FIG. 2 (b), and the adhesive laminate 2 shown in FIG. The same is true.

For example, in the adhesive laminate 1a shown in FIG. 1 (a), the peeling force at the time of peeling the peeling material on the pressure-sensitive adhesive layer (X1) and the peeling force at the time of peeling the peeling material on the pressure-sensitive adhesive layer (X2) When the peeling force is about the same, by pulling both release materials to the outside and trying to peel off, an adverse effect occurs that the adhesive laminate is separated and peeled off along with the two release materials. There is.
Therefore, the release material to be stacked on the pressure-sensitive adhesive layer (X1) and the release material to be stacked on the pressure-sensitive adhesive layer (X2) are designed to have different release forces from the pressure-sensitive adhesive layer to be attached to each other. It is preferred to use a kind of release material.

[Various physical properties of adhesive laminate]
The pressure-sensitive adhesive laminate according to one aspect of the present invention is heat treated at a temperature higher than the expansion start temperature (t) to form an interface P between the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II). It can be easily separated at once with a slight 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 the heat treatment is usually 0 to 2000 mN / 25 mm, preferably 0 to 1000 mN / 25 mm More preferably, it is 0 to 150 mN / 25 mm, more preferably 0 to 100 mN / 25 mm, still more preferably 0 to 50 mN / 25 mm.
The release force (F ₁₎ is in the case of 0 mN / 25 mm, even trying to measure the peel strength by the method described in Example, includes the case where the measurement impossible because peel strength is too small.

Further, before the heat treatment, the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive sheet (II) from the viewpoint of sufficiently fixing the processing inspection object so as not to adversely affect the processing and / or inspection work. The interlayer adhesion to the substrate (Y2) is preferably high.
From the above viewpoint, in the adhesive laminate of one aspect of the present invention, the peeling force (F ₀ ) at the time of separation at the interface P before the heat treatment is preferably 100 mN / 25 mm or more, more preferably It is 130 mN / 25 mm or more, more preferably 160 mN / 25 mm or more, and preferably 50000 mN / 25 mm or less.

In the adhesive laminate of one embodiment of the present invention, the peel force (F ₀ ) is larger than the peel force (F ₁ ). Specifically, the ratio [(F ₁ ) / (F ₀ )] between the peeling force (F ₁ ) and the peeling force (F ₀ ) is preferably 0 to 0.9, more preferably 0 to 0.8. More preferably, it is 0 to 0.5, and still more preferably 0 to 0.2.

As the temperature conditions used for measuring the peel force (F _1), there is expansion starting temperature (t) above, thermally expandable particles may be any temperature at which expansion.
As the temperature conditions used for measuring the peel force (F _0), but may be less than the expansion start temperature (t), is basically a room temperature (23 ° C.).
However, more specific measurement conditions and measurement methods of the peeling force (F ₁ ) and the peeling force (F ₀ ) are based on the method described in the examples.

In the pressure-sensitive adhesive laminate of one embodiment of the present invention, the pressure-sensitive adhesive layer (X1) (first pressure-sensitive adhesive layer (X11) and second pressure-sensitive adhesive layer (X12) possessed by the pressure-sensitive adhesive sheet (I) at room temperature (23 ° C.) And the adhesive force of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) are each independently preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2 to 8.0 N / It is preferably 25 mm, more preferably 0.4 to 6.0 N / 25 mm, still more preferably 0.5 to 4.0 N / 25 mm.
In the present specification, the adhesive force of the pressure-sensitive adhesive layers (X1) and (X2) means a value measured by the method described in the examples.

Moreover, the base material (Y1) which adhesive sheet (I) has, and the base material (Y2) which adhesive sheet (II) has are non-adhesive base materials.
In the present invention, the judgment as to whether or not the substrate is a non-adhesive substrate is made as long as the probe tack value measured in accordance with JIS Z 0237: 1991 is less than 50 mN / 5 mmφ with respect to the surface of the target substrate. The said base material is judged as a "non-adhesive base material."
The probe tack value on the surface of the substrate (Y1) of the pressure-sensitive adhesive sheet (I) used in one embodiment of the present invention and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) is each independently less than 50 mN / 5 mmφ However, it is preferably less than 30 mN / 5 mmφ, more preferably less than 10 mN / 5 mmφ, still more preferably less than 5 mN / 5 mmφ.
In addition, in this specification, the specific measuring method of the probe tack value in the surface of a thermally expandable base material is based on the method as described in an Example.

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

[Composition of adhesive sheet (I)]
The pressure-sensitive adhesive sheet (I), which the adhesive laminate of the present invention has, has a substrate (Y1) and a pressure-sensitive adhesive layer (X1), and the heat treatment causes the substrate (Y2) of the pressure-sensitive adhesive sheet (II) to It is a thermally expandable pressure-sensitive adhesive sheet including thermally expandable particles having an expansion start temperature (t) of 60 to 270 ° C. in any layer so as to be separated at the interface P.
As the pressure-sensitive adhesive sheet (I) used in one aspect of the present invention, the following one is preferable.
-Pressure-sensitive adhesive sheet (I) of the first aspect: a pressure-sensitive adhesive sheet (I) having a thermally expandable substrate layer (Y1-1) containing thermally expandable particles as a substrate (Y1).
Pressure-sensitive adhesive sheet (I) according to the second aspect: a first pressure-sensitive adhesive layer (X11) which is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles on both sides of a substrate (Y1); Pressure-sensitive adhesive sheet (I) having a second pressure-sensitive adhesive layer (X12) which is an agent layer.
Hereinafter, the adhesive sheet (I) of 1st aspect and 2nd aspect used by 1 aspect of this invention is demonstrated.

<Adhesive sheet (I) of the first embodiment>
As the pressure-sensitive adhesive sheet (I) of the first embodiment, as shown in FIGS. 1 and 2, a sheet (Y1) having a thermally expandable substrate layer (Y1-1) containing thermally expandable particles is mentioned. Be

In the pressure-sensitive adhesive sheet (I) of the first embodiment, the pressure-sensitive adhesive layer (X1) is a pressure-sensitive adhesive layer (X1) from the viewpoint of being easily separable collectively with a slight force at the interface P with the substrate (Y2) And a non-heat-expandable pressure-sensitive adhesive layer.
Specifically, in the pressure-sensitive adhesive sheet (I) possessed by the pressure-sensitive adhesive laminates 1a and 1b shown in FIG. 1, the pressure-sensitive adhesive layer (X1) is preferably a non-heat-expandable pressure-sensitive adhesive layer. Further, in the pressure-sensitive adhesive sheet (I) possessed by 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) It is preferable that it is an agent layer.

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

The thickness of the pressure-sensitive adhesive layer (X1) before the heat treatment of the pressure-sensitive adhesive sheet (I) of the first embodiment is preferably 1 to 60 μm, more preferably 2 to 50 μm, still more preferably 3 to 40 μm, still more preferably 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 (X1), the “thickness of the pressure-sensitive adhesive layer (X1)” is: The thickness of each pressure-sensitive adhesive layer (in FIG. 2, the thickness of each of the pressure-sensitive adhesive layers (X11) and (X12)) is meant.
Moreover, in this specification, the thickness of each layer which comprises an adhesive laminated body means the value measured by the method as described in an Example.

In the pressure-sensitive adhesive sheet (I) of the first embodiment, the thickness ratio of the thermally expandable base material layer (Y1-1) to the pressure-sensitive adhesive layer (X1) before the heat treatment [(Y1-1) / (X1) Is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, still more preferably 5.0 or more, and preferably 1000 or less, more preferably 200 or less. More preferably, it is 60 or less, still more preferably 30 or less.
When the thickness ratio is 0.2 or more, when the processing target is attached to the surface of the pressure-sensitive adhesive layer (X1), it is easy to prevent positional deviation of the processing target at the time of attachment. In addition, for example, as in a sealing process such as a manufacturing process of FOWLP, the surface on the target object side after sealing can be easily made flat.
Moreover, if the said thickness ratio is 1000 or less, the adhesive lamination which can be easily separated collectively by slight force by the interface P with the base material (Y2) of adhesive sheet (II) by the said heat processing It is easy to do it.

In the pressure-sensitive adhesive sheet (I) according to the first aspect, the substrate (Y1) is composed of only the thermally expandable substrate layer (Y1-1) as shown in FIG. 1 (a), The heat expandable base material layer (Y1-1) is provided on one surface side as shown in FIG. 1 (b) and the non-heat expandable base material layer (Y1-2) is provided on the other surface side. It may have the

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

<Pressure-sensitive adhesive sheet (I) of the second embodiment>
As adhesive sheet (I) of a 2nd aspect, as shown in FIG. 3, the 1st adhesive layer which is a thermally expansible adhesive layer which contains thermally expansible particle in each both sides of a substrate (Y1), respectively What has (X11) and the 2nd adhesive layer (X12) which is a non-heat-expandable adhesive layer is mentioned.
In the pressure-sensitive adhesive sheet (I) of the second embodiment, the first pressure-sensitive adhesive layer (X11), which is a thermally expandable pressure-sensitive adhesive layer, and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
In the pressure-sensitive adhesive sheet (I) of the second embodiment, the substrate (Y1) is preferably a non-thermally expandable substrate layer.

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

In the pressure-sensitive adhesive sheet (I) of the second embodiment, the thickness ratio of the first pressure-sensitive adhesive layer (X11), which is a thermally expandable pressure-sensitive adhesive layer, to the substrate (Y1) before heat treatment [(X11) / (Y1)] is preferably 0.05 to 20, more preferably 0.1 to 10, and still more preferably 0.2 to 3.

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

<Thermally expandable particles>
The thermally expandable particles used in the present invention may be particles having an expansion start temperature (t) adjusted to 60 to 270 ° C., and are appropriately selected according to the use of the adhesive laminate.
In the present specification, the expansion start temperature (t) of the thermally expandable particles means a value measured based on the following method.
[Method of measuring expansion start temperature (t) of thermally expandable particles]
0.5 mg of thermally expandable particles to be measured is added to an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, and an aluminum lid (diameter 5.6 mm, thickness 0. Prepare a sample with 1 mm).
Using a dynamic viscoelasticity measuring apparatus, measure the height of the sample while applying a force of 0.01 N to the sample from the top of the aluminum lid with a press. Then, in a state where a force of 0.01 N is applied by a pressure element, heating is performed from 20 ° C. to 300 ° C. at a temperature rising rate of 10 ° C./min, and the displacement amount in the vertical direction of the pressure element is measured. Let displacement start temperature be expansion start temperature (t).

The thermally expandable particle is a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an inclusion component which is contained in the outer shell and is vaporized when heated to a predetermined temperature. Is preferred.
Examples of the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone and the like.

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

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

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

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

<Thermally expandable substrate layer (Y1-1)>
When the substrate (Y1) of the pressure-sensitive adhesive sheet (I) of the present invention has the thermally expandable substrate layer (Y1-1) containing the thermally expandable particles, the thermally expandable substrate layer (Y1-1) is It is preferable to satisfy the following requirement (1).
Requirement (1): The storage elastic modulus E ′ (t) of the thermally expandable base material layer (Y1-1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 × 10 ⁷ Pa. It is below.
In the present specification, the storage elastic modulus E ′ of the thermally expandable base material layer (Y1-1) at a predetermined temperature means a value measured by the method described in the examples.

The above requirement (1) can be said to be an index indicating the rigidity of the thermally expandable base material layer (Y1-1) immediately before the thermally expandable particles expand.
Before the expansion of the thermally expandable particles, the temperature is increased and the storage elastic modulus E ′ of the thermally expandable base material layer (Y1-1) is decreased. However, since the thermally expandable particles begin to expand before and after reaching the expansion start temperature (t) of the thermally expandable particles, the storage elastic modulus E ′ of the thermally expandable substrate layer (Y1-1) decreases. Be suppressed.
On the other hand, heating to a temperature above the expansion start temperature (t) is necessary in order to be able to easily separate at once with a slight force at the interface P of the adhesive sheet (II) with the substrate (Y2). Therefore, it is necessary to make it easy to form asperities on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with the substrate (Y2).
That is, in the thermally expandable base material layer (Y1-1) satisfying the above requirement (1), the thermally expandable particles expand and become sufficiently large at the expansion start temperature (t), and the base material of the adhesive sheet (II) Irregularities are easily formed on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with (Y2). As a result, it is possible to form an adhesive laminate which can be easily separated at once with a slight force at the interface P of the adhesive sheet (II) with the substrate (Y2).

The storage elastic modulus E ′ (t) defined in the requirement (1) of the thermally expandable base material layer (Y1-1) used in one embodiment of the present invention is preferably 9.0 × 10 ⁶ Pa or less from the above viewpoint More preferably, it is 8.0 * 10 < ⁶ > Pa or less, More preferably, it is 6.0 * 10 < ⁶ > Pa or less, More preferably, it is 4.0 * 10 < ⁶ > Pa or less.
Moreover, the flow of the expanded thermally expandable particles is suppressed, and the shape maintainability of the unevenness formed on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with the substrate (Y2) of the pressure-sensitive adhesive sheet (II) is improved Storage elastic modulus E ′ (t) defined in the requirement (1) of the thermally expandable base material layer (Y1-1) from the viewpoint of allowing the surface P to be easily separated at once with a slight force. Preferably it is 1.0 * 10 < ³ > Pa or more, More preferably, it is 1.0 * 10 < ⁴ > Pa or more, More preferably, it is 1.0 * 10 < ⁵ > Pa or more.

In addition, the thermally expandable base material layer (Y1-1) more preferably satisfies the following requirement (2) together with the above requirement (1).
Requirement (2): The storage elastic modulus E ′ (23) of the thermally expandable base material layer (Y1-1) at 23 ° C. is 1.0 × 10 ⁶ Pa or more.

By using the thermally expandable base material layer (Y1-1) satisfying the above requirement (2), it is possible to prevent positional deviation when attaching an object such as a semiconductor chip. In addition, when the object is attached, excessive sinking to the pressure-sensitive adhesive layer can be prevented at the time of heating.

From the above viewpoint, the storage elastic modulus E ′ (23) of the thermally expandable base material layer (Y1-1) defined in the above requirement (2) is preferably 5.0 × 10 ⁶ to 5.0 × 10 ¹² Pa. , More preferably 1.0 × 10 ⁷ to 1.0 × 10 ¹² Pa, still more preferably 5.0 × 10 ⁷ to 1.0 × 10 ¹¹ Pa, still more preferably 1.0 × 10 ⁸ to 1. It is 0 × 10 ¹⁰ Pa.

From the viewpoint of providing the thermally expandable substrate layer (Y1-1) satisfying the above (1) and (2), the content of the thermally expandable particles in the thermally expandable substrate layer (Y1-1) is a thermal expansion. Relative to the total mass (100% by mass) of the base material layer (Y1-1) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, still more preferably Is 15 to 25% by mass.

From the viewpoint of improving the interlayer adhesion between the thermally expandable base material layer (Y1-1) and other layers, an oxidation method or an oxidation method is applied to the surface of the thermally expandable base material layer (Y1-1). You may perform surface treatment by the concavo-convex method etc., an easily bonding process, or a primer process.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet process), hot air treatment, ozone, and ultraviolet light irradiation treatment. Examples of the surface roughening method include sand blast method and solvent treatment method. Etc.

The thermally expandable substrate layer (Y1-1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.
In addition, the resin composition (y) may contain an additive for a base material, as needed, as long as the effects of the present invention are not impaired.
Examples of the base material additive include ultraviolet light absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, coloring agents and the like.
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 with respect to 100 parts by mass of the resin in the resin composition (y). And more preferably 0.001 to 10 parts by mass.

The thermally expandable particles contained in the resin composition (y) which is a forming material of the thermally expandable base material layer (Y1-1) are as described above.
The content of the thermally 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 components of the resin composition (y). It is up to 30% by mass, more preferably 15 to 25% by mass.

The resin contained in the resin composition (y) which is a forming material of the thermally 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 a tacky resin, the tacky resin is not in the process of forming the thermally expandable base material layer (Y1-1) from the resin composition (y). The resin obtained by the polymerization reaction with the polymerizable compound may be a non-adhesive resin, and the thermally expandable base layer (Y1-1) containing the resin may be non-adhesive.

The mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1000 to 1,000,000, more preferably 1000 to 700,000, and still more preferably 1000 to 500,000.
Moreover, when the said resin is a copolymer which has 2 or more types of structural units, the form of the said copolymer is not specifically limited, Any of a block copolymer, a random copolymer, and a graft copolymer It may be

The content of the resin is preferably 50 to 99% by mass, 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 components of the resin composition (y). %, Still more preferably 70 to 85% by mass.

From the viewpoint of forming the thermally expandable base material layer (Y1-1) satisfying the requirements (1) and (2), as the resin contained in the resin composition (y), an acrylic urethane resin and an olefin are mentioned. It is preferable to contain 1 or more types chosen from system resin.
Moreover, as said acryl urethane type resin, the following resin (U1) is preferable.
An acrylic urethane resin (U1) formed by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester.

[Acryl Urethane Resin (U1)]
As a urethane prepolymer (UP) used as the principal chain of acrylic urethane type resin (U1), the reaction product of a polyol and polyhydric isocyanate is mentioned.
In addition, it is preferable that urethane prepolymer (UP) is further what was obtained by giving chain extension reaction using a chain extender.

As a polyol used as a raw material of urethane prepolymer (UP), an alkylene type polyol, an ether type polyol, an ester type polyol, an ester amide type polyol, an ester ether type polyol, a carbonate type polyol etc. are mentioned, for example.
These polyols may be used alone or in combination of two or more.
The polyol used in one aspect of the present invention is preferably a diol, more preferably an ester type diol, an alkylene type diol and a carbonate type diol, and still more preferably an ester type diol and a carbonate type diol.

Examples of ester type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc .; ethylene glycol, propylene glycol, Alkylene glycols such as diethylene glycol and dipropylene glycol; one or more selected from diols such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hettic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexameric acid Hydrophthalic acid, There may be mentioned condensation products of one or more selected from dicarboxylic acids such as hexahydroisophthalic acid, hexahydroterephthalic acid and methylhexahydrophthalic acid, and their anhydrides.
Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methyl pentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol and polyneo A pentyl terephthalate diol etc. are mentioned.

As the alkylene type diol, for example, alkanediol such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc .; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; and polyoxyalkylene glycols such as polytetramethylene glycol.

As a carbonate type diol, for example, 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, 1,3-propylene carbonate diol 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol and the like.

Examples of the polyvalent isocyanate which is a raw material of the urethane prepolymer (UP) include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.
These polyisocyanates may be used alone or in combination of two or more.
Further, these polyvalent isocyanates may be trimethylolpropane adduct type modified bodies, Burret type modified bodies reacted with water, or isocyanurate type modified bodies containing an isocyanurate ring.

Among these, as the polyisocyanate used in one aspect of the present invention, diisocyanate is preferable, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 More preferred is one or more selected from tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.

As alicyclic diisocyanate, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentadiisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane Diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc. may be mentioned, and isophorone diisocyanate (IPDI) is preferred.

In one embodiment of the present invention, the urethane prepolymer (UP) to be 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 an ethylenically unsaturated group at both ends Urethane prepolymers are preferred.
As a method of introducing an ethylenically unsaturated group at both ends of the linear urethane prepolymer, an NCO group at the end of the linear urethane prepolymer formed by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And the method of making it react.

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

The vinyl compound to be the side chain of the acrylic urethane resin (U1) contains at least (meth) acrylic acid ester.
As a (meth) acrylic acid ester, 1 or more types chosen from an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate are preferable, and it is more preferable to use together an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.

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

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

Moreover, as a hydroxyalkyl (meth) acrylate, the same thing as the hydroxyalkyl (meth) acrylate used in order to introduce | transduce an ethylenically unsaturated group into the both terminal of the above-mentioned linear urethane prepolymer is mentioned.

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

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

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

In the acrylic urethane resin (U1) used in one embodiment of the present invention, the content ratio of the structural unit (u11) derived from the urethane prepolymer (UP) to 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, still more preferably 35 by mass ratio. / 65 to 55/45.

[Olefin resin]
As an olefin resin suitable as resin contained in a resin composition (y), it is a polymer which has a structural unit derived from an olefin monomer at least.
The above-mentioned 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), polyethylene resins such as linear low density polyethylene; (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); ethylene -Vinyl alcohol copolymer (EVOH); ethylene-propylene And olefin-based ternary copolymers such as-(5-ethylidene-2-norbornene).

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

For example, as an acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin, a modified polymer obtained by graft polymerizing unsaturated carboxylic acid or its anhydride with the above-mentioned non-modified olefin-based resin Can be mentioned.
Examples of the above-mentioned unsaturated carboxylic acids or their anhydrides include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride And glutaconic anhydride, citraconic anhydride, aconitic acid anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride and the like.
In addition, unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.

As an acrylic modified olefin resin formed by subjecting an olefin resin to acrylic modification, a modified polymer obtained by graft polymerizing alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin which is the main chain Polymers may be mentioned.
The number of carbon atoms of the alkyl group contained in the above alkyl (meth) acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12.
As said alkyl (meth) acrylate, the same thing as the compound which can be selected as a below-mentioned monomer (a1 ') is mentioned, for example.

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

(Resin other than acrylic urethane resin and olefin resin)
In one aspect of the present invention, the resin composition (y) may contain a resin other than the acrylic urethane resin and the olefin resin, as long as the effects of the present invention are not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer Polymer; triacetate cellulose; polycarbonate; polyurethane not corresponding to acrylic urethane resin; polysulfone; polyetheretherketone; polyethersulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; A fluorine resin etc. may be mentioned.

However, from the viewpoint of forming the thermally expandable base material layer (Y1-1) satisfying the above requirements (1) and (2), resins other than acrylic urethane resin and olefin resin in the resin composition (y) The content ratio is preferably smaller.
The content ratio of resins other than acrylic urethane resins and olefin resins 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 resins contained in the resin composition (y). It is less than 10 parts by weight, more preferably less than 5 parts by weight, and even more preferably less than 1 part by weight.

[Solvent-free type 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 The solvent-free resin composition (y1) which contains particles and does not contain a solvent is mentioned.
In the non-solvent type resin composition (y1), although the solvent is not blended, the energy ray polymerizable monomer contributes to the improvement of the plasticity of the oligomer.
A thermally expandable base material layer (Y1-1) satisfying the above requirements (1) and (2) is formed by irradiating the coating film formed of the solvent-free resin composition (y1) with an energy ray. Easy to do.

In addition, about the kind of the thermally expansible particle | grains mix | blended with a non-solvent type resin composition (y1), a shape, and compounding quantity (content), it is as above-mentioned.

The mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50000 or less, preferably 1000 to 50000, more preferably 2000 to 40000, still more preferably 3000 to 35000, More preferably, it is 4000 to 30000.

Moreover, as the above-mentioned oligomer, among resins contained in the above-mentioned resin composition (y), those having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less may be used. Is preferred.
In addition, as the said oligomer, the modified olefin resin which has an ethylenically unsaturated group can also be used.

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

Examples of energy ray polymerizable monomers include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantane ( Alicyclic polymerizable compounds such as meta) acrylate and tricyclodecane acrylate; aromatic polymerizable compounds such as phenyl hydroxy propyl acrylate, benzyl acrylate and phenol ethylene oxide modified acrylate; tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N- Examples thereof include heterocyclic polymerizable compounds such as vinyl pyrrolidone and N-vinyl caprolactam.
These energy beam polymerizable monomers may be used alone or in combination of two or more.

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

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

As the photopolymerization initiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyrol Nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone and the like can be mentioned.
These photopolymerization initiators may be used alone or in combination of two or more.

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

<Non-Thermally Expandable Substrate Layer (Y1-2)>
Examples of the material for forming the non-thermally expandable substrate layer (Y1-2) constituting the substrate (Y1) include paper materials, resins, metals and the like, and the adhesive laminate of one aspect of the present invention It can select suitably according to a use.

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

These forming materials may be comprised by 1 type, and may use 2 or more types together.
As a non-thermally expandable substrate layer (Y1-2) using two or more kinds of forming materials in combination, a paper material is laminated with a thermoplastic resin such as polyethylene, or a metal film on the surface of a resin film or sheet containing a resin What formed the film etc. are mentioned.
In addition, as a formation method of a metal layer, the method of vapor-depositing said metal by PVD methods, such as vacuum evaporation, sputtering, and ion plating, for example, or sticking metal foil consisting of said metal using a general adhesive And the like.

When the non-heat-expandable base layer (Y1-2) contains a resin, the non-heat-expandable base layer (Y1-2) contains a resin from the viewpoint of improving the interlayer adhesion between the non-heat-expandable base layer (Y1-2) and other layers laminated. Also on the surface of the thermally expandable base material layer (Y1-2), as in the case of the above-mentioned thermally expandable base material layer (Y1-1), surface treatment by an oxidation method or a roughening method, adhesion treatment, Alternatively, primer treatment may be performed.

In addition, when the non-thermally expandable substrate layer (Y1-2) contains a resin, it may contain the above-mentioned additive for a substrate that can be contained in the resin composition (y) together with the resin.

The non-thermally expandable substrate layer (Y1-2) is a non-thermally expandable layer judged based on the above-mentioned method.
Therefore, the volume change rate (%) of the non-heat-expandable substrate layer (Y1-2) calculated from the above equation is less than 5%, preferably less than 2%, more preferably less than 1% More preferably, it is less than 0.1%, still more preferably less than 0.01%.

Further, the non-thermally expandable substrate layer (Y1-2) may contain thermally expandable particles as long as the volume change rate is in the above range. For example, by selecting the resin contained in the non-heat-expandable substrate layer (Y1-2), it is possible to adjust the volume change rate to the above-mentioned range even if the heat-expandable particles are contained. .
However, the content of the thermally expandable particles in the non-thermally expandable substrate layer (Y1-2) is preferably as small as possible.
The specific content of the thermally 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-thermally expandable substrate layer (Y1-2). More preferably, it is less than 0.1% by mass, still more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass.

<Pressure-sensitive adhesive layer (X1)>
The pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) used in one aspect of the present invention can be formed from a pressure-sensitive adhesive composition (x1) containing a pressure-sensitive adhesive resin.
The pressure-sensitive adhesive composition (x1) may contain, if necessary, an additive for a pressure-sensitive adhesive such as a crosslinking agent, a tackifier, a polymerizable compound, or a polymerization initiator.

<Adhesive resin>
The adhesive resin used in one aspect 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 2,000,000, more preferably 20,000 to 1,500,000, and still more preferably 30,000 from the viewpoint of improving the adhesive strength. ~ 1 million.

The content of the adhesive resin is preferably 30 to 99 based on the total amount (100% by mass) of the active ingredients of the adhesive composition (x1) or the total mass (100% by mass) of the adhesive layer (X1). .99% by mass, more preferably 40 to 99.95% by mass, still more preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, still more preferably 60 to 99.50% by mass It is.

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 tackifying resins may be used alone or in combination of two or more.
Moreover, when these adhesive resins are copolymers which have 2 or more types of structural units, the form of the said copolymer is not specifically limited, A block copolymer, a random copolymer, and graft co It may be any of 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 to the side chain of the above-mentioned adhesive resin.
Examples of the polymerizable functional group include (meth) acryloyl group and vinyl group.
Moreover, although an ultraviolet-ray and an electron beam are mentioned as an energy ray, an ultraviolet-ray is preferable.

In one aspect of the present invention, the surface of the pressure-sensitive adhesive layer (X1) in contact with the pressure-sensitive adhesive sheet (II) has unevenness due to expansion of the thermally expandable particles by heat treatment, from the viewpoint of exhibiting excellent adhesion. From the viewpoint of facilitating formation, it is preferable that the adhesive resin contains an acrylic resin.
The content ratio of the acrylic resin in the adhesive resin is preferably 30 to 100 based on the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x1) or the adhesive layer (X1). % By mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass.

(Acrylic resin)
In one embodiment of the present invention, as an acrylic resin that can be used as a tacky resin, for example, a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, a cyclic structure The polymer etc. which contain the structural unit derived from the (meth) acrylate which has these are mentioned.

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 still more preferably 500,000 to 1,100,000. .

As an acrylic resin used in one aspect of the present invention, 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) The 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 of the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and still more preferably 4 to 8 from the viewpoint of improving adhesion properties. It is.
In addition, the alkyl group which a monomer (a1 ') has may be a linear alkyl group, and a branched alkyl group may be sufficient.

As the monomer (a1 ′), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Meta) acrylate, stearyl (meth) acrylate, etc. are mentioned.
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 mass%, more preferably 60 to 99.0 mass based on the total structural units (100 mass%) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, still more preferably 80 to 95.0% by mass.

As a functional group which a monomer (a2 ') has, a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. are mentioned, for example.
That is, as a monomer (a2 '), a hydroxyl-containing monomer, a carboxy-group containing monomer, an amino-group containing monomer, an epoxy-group containing monomer etc. are mentioned, for example.
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.

As a hydroxyl-containing monomer, the same thing as the hydroxyl-containing compound mentioned above is mentioned, for example.

Examples of carboxy group-containing monomers include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; and ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof And 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, relative to the total constituent units (100% by mass) of the acrylic copolymer (A1). %, More preferably 1.0 to 30% by mass, and still more preferably 3.0 to 25% by mass.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from another 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% of the total structural units (100% by mass) of the acrylic copolymer (A1). It is about -100% by mass, more preferably 80-100% by mass, still more preferably 90-100% by mass, still more preferably 95-100% 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-based monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylate, Has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, imide (meth) acrylate (Meth) acrylate; styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloyl Ruhorin, N- vinylpyrrolidone and the like.

The acrylic copolymer (A1) may be an energy ray-curable acrylic copolymer in which a polymerizable functional group is introduced into the side chain.
The polymerizable functional group and the energy ray are as described above.
The polymerizable functional group is a substituent capable of binding to the acrylic copolymer having the above-mentioned structural units (a1) and (a2) and the functional group possessed by the structural unit (a2) of the acrylic copolymer It can introduce | transduce by making the compound which has, and a polymerizable functional group react.
Examples of the compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, glycidyl (meth) acrylate and the like.

<Crosslinking agent>
In one embodiment of the present invention, the pressure-sensitive adhesive composition (x1) may further contain a crosslinking agent when it contains a pressure-sensitive resin having a functional group as in the above-mentioned acrylic copolymer (A1). preferable.
The said crosslinking agent reacts with the adhesive resin which has a functional group, and bridge | crosslinks adhesive resin, making the said functional group a crosslinking origin.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned, for example.
These crosslinking agents may be used alone or in combination of two or more.
Among these crosslinking agents, isocyanate-based crosslinking agents are preferable from the viewpoint of enhancing the cohesion and improving the adhesiveness, and from the viewpoint of availability and the like.

The content of the crosslinking agent is appropriately adjusted according to the number of functional groups possessed by the adhesive resin, but is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having a functional group. The amount is more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.

<Tackifier>
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 term "tackifier" refers to a component that aids in improving the adhesive strength of the above-mentioned tacky resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, It is to be distinguished from the sexing resin.
The mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 500 to 8000, and still more preferably 800 to 5000.

The tackifier is obtained, for example, by copolymerizing a rosin resin, a terpene resin, a styrene resin, a penten formed by thermal decomposition of petroleum naphtha, a C5 fraction such as isoprene, piperine, 1,3-pentadiene and the like. C5 petroleum resins, indene formed by thermal decomposition of petroleum naphtha, C9 petroleum resins obtained by copolymerizing C9 fractions such as vinyl toluene, and hydrogenated resins obtained by hydrogenating these.

The softening point of the tackifier is preferably 60 to 170 ° C., more preferably 65 to 160 ° C., still 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 or structures may be used in combination.
And when using 2 or more types of multiple tackifiers, it is preferable that the weighted average of the softening point of these multiple tackifiers belongs to the said range.

The content of the tackifier is preferably 0.01 to 100 parts by mass with respect to the total amount (100% by mass) of the active ingredients of the pressure-sensitive adhesive composition (x1) or the total mass (100% by mass) of the 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.

<Photoinitiator>
In one aspect of the present invention, when the pressure-sensitive adhesive composition (x1) contains an energy ray-curable adhesive resin as the adhesive resin, it is preferable to further contain a photopolymerization initiator.
In particular, it is preferable that the pressure-sensitive adhesive composition forming the non-heat-expandable pressure-sensitive adhesive layer on the side to which the processing and inspection object is attached contains an energy ray-curable adhesive resin and a photopolymerization initiator.
A pressure-sensitive adhesive layer (X1) formed of a pressure-sensitive adhesive composition containing such an energy ray-curable adhesive resin and a photopolymerization initiator has a sufficiently curing reaction by irradiation of energy rays of relatively low energy It is possible to proceed and adjust the tack to the desired range.
For example, at the time of the heat treatment, good adhesion with the object to be processed and inspected is maintained, but after separation at the interface P, after performing a predetermined treatment, it is desirable to remove from the adhesive sheet (I) from the object to be processed and inspected In this case, the processing inspection object and the pressure-sensitive adhesive sheet (I) can be easily separated by irradiating the energy beam.
In addition, as a photoinitiator, the same thing as what is mix | blended with the above-mentioned non-solvent type resin composition (y1) is mentioned.

The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.1 parts by mass with respect to 100 parts by mass of the energy ray-curable adhesive resin. It is 05 to 2 parts by mass.

<Additives for adhesive>
In one embodiment 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 effects of the present invention are not impaired. It may be done.
Examples of such an adhesive additive include an antioxidant, a softener (plasticizer), a rust inhibitor, a pigment, a dye, a retarder, a reaction accelerator (catalyst), an ultraviolet absorber, and the like.
These pressure-sensitive adhesive additives may be used alone or in combination of two or more.

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

In addition, when using adhesive sheet (I) of the above-mentioned 2nd aspect as shown in FIG. 3, the 1st adhesive layer (X11) which is a heat-expandable adhesive layer contains heat-expandable particle | grains further. It is formed from a thermally expandable pressure-sensitive adhesive composition (x11).
The thermally expandable particles are as described above.
The content of the thermally expandable particles is preferably based on the total amount (100% by mass) of the active components of the thermally expandable pressure-sensitive adhesive composition (x11) or the total mass (100% by mass) of the thermally expandable pressure-sensitive adhesive layer Is preferably 1 to 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and still more preferably 5 to 40% by mass.

On the other hand, when the pressure-sensitive adhesive layer (X1) is a non-heat-expandable pressure-sensitive adhesive layer, the heat-expandable particles in the non-heat-expandable pressure-sensitive adhesive composition (x12) which is a forming material of the non-heat-expandable pressure-sensitive adhesive layer The content is preferably as small as possible.
The content of the thermally expandable particles is based on the total amount (100% by mass) of the active ingredients of the non-thermally expandable adhesive composition (x12) or the total mass (100% by mass) of the non-thermally expandable adhesive layer Preferably, it is less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass.

When the pressure-sensitive adhesive layer (X1) is a non-heat-expandable pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer (X1) is a surface to which a processing inspection object is attached, the non-heat-expandable pressure-sensitive adhesive layer at 23 ° C. The storage shear modulus G ′ (23) of a certain pressure-sensitive adhesive layer (X1) is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 × 10 ⁴ Pa or more, still more preferably 1.0 × 10 4 ^{It is 5} Pa or more. Also, it is usually 1.0 × 10 ⁸ Pa or less.
If the storage shear elastic modulus G '(23) of the pressure-sensitive adhesive layer (X1) which is a non-thermal expansion pressure-sensitive adhesive layer is 1.0 × 10 ⁴ Pa or more, the processing inspection object is performed on the surface of the pressure-sensitive adhesive layer (X1) It is easy to prevent the positional deviation at the time of sticking an object, and also to prevent the excessive sinking to the adhesive layer (X1) at that time.
If the storage shear elastic modulus G ′ (23) of the pressure-sensitive adhesive layer (X1) which is a non-heat-expandable pressure-sensitive adhesive layer is 1.0 × 10 ⁸ Pa or less, for example, the adhesive laminate 1c shown in FIG. The pressure-sensitive adhesive layer (X1) being in contact with the pressure-sensitive adhesive sheet (II) by the expansion of the thermally expandable particles in the thermally expandable base material layer (Y1-1) by the heat treatment when the constitution is 1d. Irregularities are easily formed on the surface of As a result, it is possible to obtain an adhesive laminate which can be easily separated at one time with a slight force at the interface P of the adhesive sheet (II) with the substrate (Y2).
When the pressure-sensitive adhesive layer (X1) is a non-heat-expandable pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer (X1) is a surface to which a support is attached, the non-heat-expandable pressure-sensitive adhesive layer at 23 ° C. The storage shear modulus G ′ (23) of a certain pressure-sensitive adhesive layer (X1) is preferably 1.0 × 10 ⁴ to 1.0 × 10 ⁸ Pa, from the viewpoint of making the adhesion to the support good. It is preferably 3.0 × 10 ⁴ to 5.0 × 10 ⁷ Pa, more preferably 5.0 × 10 ⁴ to 1.0 × 10 ⁷ Pa.
A pressure-sensitive adhesive sheet (I) having a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12) which is a non-swelling pressure-sensitive adhesive layer as in the pressure-sensitive adhesive laminates 1c and 1d shown in FIG. The storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11), which is a non-intumescent pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁸ Pa or less, more preferably It is 5.0 × 10 ⁷ Pa or less, more preferably 1.0 × 10 ⁷ Pa or less.
If 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, is 1.0 × 10 ⁸ Pa or less, for example, the adhesive laminate shown in FIG. The first pressure-sensitive adhesive in contact with the pressure-sensitive adhesive sheet (II) due to the expansion of the thermally expandable fine particles in the thermally expandable base material layer (Y1-1) by the heat treatment when it is configured as 1c, 1d Irregularities are easily formed on the surface of the layer (X11). As a result, it is easy to obtain an adhesive laminate which can be easily separated at one time with a slight force at the interface P of the adhesive sheet (II) with the substrate (Y2).
The storage shear modulus G ′ (23) of the second pressure-sensitive adhesive layer (X12), which is a non-expanding pressure-sensitive adhesive layer, at 23 ° C. is the same as that of the pressure-sensitive adhesive layer (X1), but the non-expandable pressure-sensitive adhesive layer Storage shear modulus G '(23) of the second pressure-sensitive adhesive layer (X12) which is a non-swelling pressure-sensitive adhesive layer rather than storage shear modulus G' (23) of the first pressure-sensitive adhesive layer (X11) Is preferably high. As a result, asperities are more easily formed on the surface of the first pressure-sensitive adhesive layer (X11) than on the surface of the second pressure-sensitive adhesive layer (X12), and slightly at the interface P of the pressure-sensitive adhesive sheet (II) with the substrate (Y2) It is easy to make an adhesive laminate that can be separated easily and collectively with a force.
In addition, in this specification, storage shear elastic modulus G '(23) of an adhesive layer means the value measured by the method as described in an Example.

[Composition of adhesive sheet (II)]
The adhesive sheet (II) of the adhesive laminate of the present invention has a substrate (Y2) and an adhesive layer (X2) on one surface side of the substrate (Y2), and the substrate (Y2) The other surface side of is directly laminated with the adhesive sheet (I).
From the viewpoint of improving the interlayer adhesion between the substrate (Y2) and the pressure-sensitive adhesive layer (X2), the above-mentioned oxidation method and unevenness forming method are provided on the surface of the substrate (Y2) on which the pressure-sensitive adhesive layer is laminated. Surface treatment by adhesion etc., easy adhesion treatment, or primer treatment may be applied.

The base material (Y2) is preferably a non-heat-expandable base material, from the viewpoint of being able to be easily separated at once with a slight force at the interface P with the pressure-sensitive adhesive sheet (I).
Moreover, before and after the heat treatment, the pressure-sensitive adhesive layer (X2) is also preferably a non-heat-expandable pressure-sensitive adhesive layer from the viewpoint of maintaining good adhesion to the adherend.
Therefore, the volume change rate (%) of the substrate (Y2) and the pressure-sensitive adhesive layer (X2) calculated from the above-mentioned formula is each independently less than 5%, preferably less than 2%, more preferably Is less than 1%, more preferably less than 0.1%, still more preferably less than 0.01%.

Examples of the forming material of the base (Y2) include the same as the forming materials of the above-mentioned non-heat-expandable base layer (Y1-2).
From the viewpoint of improving adhesion to the pressure-sensitive adhesive sheet (I) before the heat treatment, and at the interface P at the time of the heat treatment, the substrate (Y2) can be easily separated at once with a slight force It is preferable to contain a resin, and it is more preferable that a resin layer containing a resin is formed on the surface of the base (Y2) on the side laminated with at least the pressure-sensitive adhesive sheet (I). More preferably, it is a film or a sheet.

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

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

The pressure-sensitive adhesive layer (X2) can be formed from a pressure-sensitive adhesive composition (x2) containing a pressure-sensitive adhesive resin.
The pressure-sensitive adhesive composition (x2) may contain, if necessary, an additive for a pressure-sensitive adhesive such as a crosslinking agent, a tackifier, a polymerizable compound, or a polymerization initiator.
The adhesive resin and the adhesive additive contained in the pressure-sensitive adhesive composition (x2) are the same as those contained in the pressure-sensitive adhesive composition (x1) which is a forming material of the above-mentioned pressure-sensitive adhesive layer (X1). The preferable range of the content of suitable components and each component is also the same.

When the pressure-sensitive adhesive composition (x2) contains an energy ray-curable adhesive resin as the adhesive resin, the adhesive composition (x2) may further contain a photopolymerization initiator.
In the case of a pressure-sensitive adhesive layer (X2) formed of a pressure-sensitive adhesive composition (x2) containing a photopolymerization initiator, after being attached to an adherend, the adherend is easily attached by irradiating energy beam. It can be separated.
In addition, as an energy ray-curable adhesive resin and a photoinitiator, it is as above-mentioned.

The pressure-sensitive adhesive layer (X2) may contain thermally expandable particles as long as the volume change rate is in the above range, but the content of the thermally expandable particles in the pressure-sensitive adhesive layer (X2) is preferably as small as possible. .
The content of the thermally expandable particles is usually 3% by mass with respect to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x2) or the total mass (100% by mass) of the adhesive layer (X2) It is less than, preferably less than 1% by weight, more preferably less than 0.1% by weight, still more preferably less than 0.01% by weight, still more preferably less than 0.001% by weight.

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

When the pressure-sensitive adhesive layer (X2) is a non-heat-expandable pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer (X2) is a surface to which a processing inspection object is attached, the non-heat-expandable pressure-sensitive adhesive layer at 23 ° C. The storage shear modulus G ′ (23) of a certain pressure-sensitive adhesive layer (X2) is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 × 10 ⁴ Pa or more, still more preferably 1.0 × 10 4 ^{It is 5} Pa or more. Also, it is usually 1.0 × 10 ⁸ Pa or less.
If the storage shear elastic modulus G '(23) of the pressure-sensitive adhesive layer (X2) which is a non-thermal expansion pressure-sensitive adhesive layer is 1.0 × 10 ⁴ Pa or more, the processing inspection object is performed on the surface of the pressure-sensitive adhesive layer (X2) It is easy to prevent the positional deviation at the time of sticking a thing, and it is easy to prevent the excessive sinking to the adhesive layer (X2) in that case.
When the pressure-sensitive adhesive layer (X2) is a non-heat-expandable pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer (X2) is a surface to which a support is attached, the non-heat-expandable pressure-sensitive adhesive layer at 23 ° C. The storage shear modulus G ′ (23) of a certain pressure-sensitive adhesive layer (X2) is preferably 1.0 × 10 ⁴ to 1.0 × 10 ⁸ Pa, from the viewpoint of making the adhesion to the support good. It is preferably 3.0 × 10 ⁴ to 5.0 × 10 ⁷ Pa, more preferably 5.0 × 10 ⁴ to 1.0 × 10 ⁷ Pa.

<Peeling material>
In the pressure-sensitive adhesive laminate of one embodiment 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 adherend.
As the peeling material, a peeling sheet subjected to double-sided peeling treatment, a peeling sheet subjected to single-sided peeling treatment, and the like are used, and examples thereof include those obtained by applying a peeling agent on a substrate for peeling material.

Examples of substrates for release materials include papers such as high-quality paper, glassine paper, kraft paper, etc .; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, olefins such as polypropylene resin, polyethylene resin Plastic films, such as a resin film ;; etc. are mentioned.

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

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

[Method of using adhesive laminate]
The adhesive laminate of the present invention can easily separate the processed inspection object with a slight force after attaching the processed inspection object and carrying out the processing and / or inspection. In the process, the work of attaching a new adhesive sheet to the processing inspection object after separation can be omitted.
As a method of using the pressure-sensitive adhesive laminate of the present invention in which the above matters are reflected, for example, a method of using the following steps (1) to (3) can be mentioned.
Step (1): A processing and inspection object is fixed to a support via the adhesive laminate of the present invention, and the support, the adhesive laminate, and the processing and inspection object are laminated in this order. Process.
Step (2): a step of processing and / or inspecting the object to be processed and inspected.
Step (3): Separation at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) Process.
Hereinafter, steps (1) to (3) will be described with reference to FIGS. 4 and 5 as appropriate.
Incidentally, “fixing the processing inspection object to the support via the adhesive laminate of the present invention” means attaching the processing inspection object to the support via the adhesive laminate of the present invention. Specifically, it means that the object to be processed and inspected is attached to one side of the adhesive laminate and the support is attached to the other side.

<Step (1)>
(A) of FIG. 4 and 5 is a cross-sectional schematic diagram which shows the state which fixed the process inspection target object to the support body through the adhesive laminated body of this invention.
In the step (1), as shown in (a) of FIGS. 4 and 5, the processing inspection object 60 is fixed to the support 50 via the adhesive laminate 1a of the present invention, and the support, the adhesion Laminate and the processing and inspection object are laminated in this order.
In addition, although the example using the adhesive laminated body 1a shown to Fig.1 (a) is shown in FIG. 4 and 5, also when using the adhesive laminated body of this invention which has another structure, it is the same. Then, the support, the adhesive laminate, and the processing inspection object are laminated in this order.

As shown in FIG. 4 (a), in this step (1), the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate and the support are attached, and the pressure-sensitive adhesive laminate By sticking the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the present invention and the processing inspection object, the processing inspection object may be fixed to the support via the adhesive laminate.
Alternatively, as shown in FIG. 5 (a), in this step (1), the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the support are attached to each other. By sticking the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the laminate and the object to be processed and inspected, the object to be processed and inspected may be fixed to the support via the adhesive laminate. Good.

In addition, as a process test object affixed to an adhesive laminated body, a semiconductor chip, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a LED element, a sapphire board, a display, the board | substrate for panels etc. are mentioned, for example.

The said support body is used in order to fix a process inspection target object in process (2), and to raise the precision of a process or a test | inspection.
The support is preferably attached to the entire surface of the pressure-sensitive adhesive layer (X1) or (X2) of the pressure-sensitive adhesive laminate.
Therefore, the support is preferably in the form of a plate. Also, as shown in FIGS. 4 and 5, the surface area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2) and the surface of the support to which the pressure-sensitive adhesive layer is attached is the adhesion of the pressure-sensitive adhesive layer (X1) or (X2) It is preferable that it is more than the area of the surface 122a.

As the material constituting the support, in consideration of the required characteristics such as mechanical strength and heat resistance depending on the type of object to be processed and inspected and the processing or inspection to be performed in the step (2), appropriate It is selected.
Specific materials constituting the support include, for example, metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafer; epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic, polyimide resin, Resin materials, such as polyamide imide resin; Composite materials, such as glass epoxy resin, etc. are mentioned, Among these, SUS, glass, a silicon wafer, etc. are preferred.
Examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
Super engineering plastics include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).

The thickness of the support is appropriately selected in consideration of required properties 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 step (1) may be less than the expansion start temperature (t) of the thermally expandable particles, but under an environment of 0 to 80 ° C. (the expansion start temperature (t) is 60 to 80 ° C. In some cases, it is preferable to be performed under an environment below the expansion start temperature (t).

<Step (2)>
At a process (2), a process and / or test | inspection is given with respect to the said process inspection object affixed on the adhesive layer (X1) or (X2) of the adhesive laminated body of this invention at a process (1).
Examples of processing to be performed in the step (2) include sealing processing on an object using a resin, grinding processing on the object, dicing (dividing) processing, circuit formation processing, etching processing, plating processing, sputtering processing , Vapor deposition treatment, protective film formation treatment, lamination treatment using an adhesive sheet prepared separately, and the like.
Moreover, as an inspection process given at a process (2), the automatic optical inspection (AOI) etc. which confirm the presence or absence of die shift, a chipping, etc. are mentioned, for example.
In this step (2), two or more of these processing and inspection may be performed in combination.

The temperature condition in the step (1) may be less than the expansion start temperature (t) of the thermally expandable particles, but it is preferable to be carried out under an environment of 0 to 50 ° C.

<Step (3)>
In the step (3), separation is performed at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the base material (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t). Do.
(B) of FIG. 4 and 5 is a cross-sectional schematic diagram which shows the state isolate | separated by the interface P by heat processing.
FIG. 4B shows a state in which the object to be processed and inspected is separated in the state of being laminated on the pressure-sensitive adhesive sheet (I) by the heat treatment.
Moreover, in FIG.5 (b), the state which isolate | separated in the state which the process test target object laminated | stacked on adhesive sheet (II) by the said heat processing is shown.

As "a temperature above expansion start temperature (t)" at the time of heat treatment in the step (3), it is "expansion start temperature (t) + 10 ° C" or more and "expansion start temperature (t) + 60 ° C" or less It is more preferable that "expansion start temperature (t) + 15 degreeC" or more and "expansion start temperature (t) + 40 degreeC" or less.

Thus, since the processing inspection object with a pressure sensitive adhesive sheet can be obtained, the work which sticks a new pressure sensitive adhesive sheet on the processing inspection object after separation can be omitted at the next process.
The adhesive laminate of the present invention used as described above can be used for the production of various products, but it is preferably used, for example, in the method for producing a semiconductor device as described below.

[Method of Manufacturing Semiconductor Device]
A semiconductor device can be manufactured using the adhesive laminate of the present invention, and specifically, a method for manufacturing a semiconductor device having the following steps (i) to (iii) can be mentioned.
Step (i): The pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the pressure-sensitive adhesive surface (X2) of the pressure-sensitive adhesive sheet (II) And attaching the semiconductor chip to a part of the other adhesive surface.
Step (ii): covering the semiconductor chip and the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2) of at least the periphery of the semiconductor chip with a sealing material, and curing the sealing material, A step of obtaining a cured sealing body in which the semiconductor chip is sealed in a curing sealing material.
Step (iii): Separation at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) And a step of obtaining a cured seal with a pressure-sensitive adhesive sheet, wherein the cured seal is laminated on the pressure-sensitive adhesive sheet (I) or (II).

<Step (i)>
The step (i) comprises the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate and the support It is a process of sticking and mounting a semiconductor chip on a part of the other adhesive surface.
In this step, as shown in FIG. 4A, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) and the support 50 are attached to each other, and the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) The semiconductor chip 60 may be placed on a part of the adhesive surface of
Further, as shown in FIG. 5 (a), the adhesive surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the support 50 are attached, and the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is adhered The semiconductor chip 60 may be mounted on part of the surface.

The support used in step (i) is as described above.
Further, as the semiconductor chip, conventionally known ones 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.
And it is preferable to be mounted so that the circuit surface of a semiconductor chip may be covered with the adhesive surface of the adhesive layer (X1) of adhesive sheet (I). A known device such as a flip chip bonder or a die bonder can be used to mount the semiconductor chip.
The layout of the arrangement of the semiconductor chips, the number of arrangement, and the like may be appropriately determined in accordance with the form of the target package, the number of production, and the like.

Here, as a method of manufacturing a semiconductor device according to one aspect of the present invention, a semiconductor chip is covered with a sealing material such as FOWLP, FOPLP, etc. in a region larger than the chip size, and not only the circuit surface of the semiconductor chip It is preferable to apply to the package which forms a redistribution layer also in the surface area | region of a sealing material.
Therefore, the semiconductor chip is placed on a part of the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2), and the plurality of semiconductor chips are aligned with a predetermined distance therebetween. The semiconductor chip CP is preferably mounted on the adhesive surface, and the plurality of semiconductor chips CP are mounted on the adhesive surface in a state of being aligned in a matrix of plural rows and plural columns at a predetermined interval. preferable.
The distance between the semiconductor chips may be appropriately determined in accordance with the form of the target package and the like.

<Step (ii)>
The step (ii) covers the semiconductor chip and the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2) of at least the peripheral portion of the semiconductor chip with a sealing material (hereinafter, also referred to as "coating step") And a step of curing the sealing material to obtain a cured sealing body in which the semiconductor chip is sealed with the cured sealing material (hereinafter, also referred to as a “curing step”).
For example, as shown in FIG. 4A, when the semiconductor chip 60 is placed on a part of the adhesive surface of the pressure-sensitive adhesive layer (X1) in the previous step (i), the pressure-sensitive adhesive layer (X1) is Of the adhesive surface, the peripheral portion of the semiconductor chip is formed.
That is, the peripheral portion of the semiconductor chip refers to the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2) corresponding to the gap between adjacent semiconductor chips among a plurality of semiconductor chips.

In the covering step of the step (ii), first, the semiconductor chip and the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2), the peripheral portion of the semiconductor chip is covered with a sealing material. The sealing material is filled in the gaps between the plurality of semiconductor chips while covering the entire exposed surface of the semiconductor chips.

The sealing material has a function of protecting the semiconductor chip and the components attached thereto from the external environment.
As a sealing material, arbitrary things can be selected suitably and used from what is used as a semiconductor sealing material, for example, the sealing material containing a thermosetting resin, and energy ray curable resin And the like.
The sealing material may be solid such as granular or sheet at room temperature, or may be liquid in the form of a composition, but from the viewpoint of workability, a sheet-like sealing material Is preferred.

As a method of covering a semiconductor chip and its peripheral part using a sealing material, it selects suitably according to the kind of sealing material from the methods conventionally applied to the semiconductor sealing process, and is applied. 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 method, and the like can be applied.

Then, after performing the covering step, the sealing material is cured to obtain a cured sealing body in which the semiconductor chip is sealed with the curing sealing material.
In addition, it is preferable that the coating process and hardening process of process (ii) are performed on temperature conditions less than the expansion start temperature (t) of thermally expansible particle | grains.
Moreover, although a coating process and a hardening process may be implemented separately, when heating a sealing material in a coating process, a sealing material is hardened as it is by the heating, and a coating process and a hardening process May be implemented simultaneously.

<Step (iii)>
Step (iii) separates at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) The step is to obtain a cured sheet with a pressure-sensitive adhesive sheet formed by laminating the cured sheet on the pressure-sensitive adhesive sheet (I) or (II).
As a result of the heat treatment, the thermally expandable particles expand, and asperities are generated on the surface of the pressure-sensitive adhesive sheet (I) on the side of the substrate (Y2) of the pressure-sensitive adhesive sheet (II). As a result, it can be easily separated collectively at a slight force at the interface P.
The temperature conditions of the heat treatment in the step (iii) are as described above.

In the step (i), when the semiconductor chip is placed on a part of the adhesive surface of the adhesive layer (X1) of the adhesive sheet (I), the adhesive sheet (I) on the adhesive layer (X1) The pressure-sensitive adhesive sheet-attached cured and sealed article can be obtained by laminating the cured and sealed article on one another.
In the step (i), when the semiconductor chip is placed on a part of the adhesive surface of the adhesive layer (X2) of the adhesive sheet (II), the adhesive sheet (II) on the adhesive layer (X2) The pressure-sensitive adhesive sheet-attached cured and sealed article can be obtained by laminating the cured and sealed article on one another.

The following steps (iv) to (vii) may be mentioned as the next step carried out using the pressure-sensitive adhesive sheet-attached cured sealing body thus obtained.
Step (iv): a step of grinding the cured sealing body and adjusting the thickness of the cured sealing body.
Step (v): a step of forming a rewiring layer on the cured package.
Step (vi): A step of forming an external electrode pad on the cured sealing body, and connecting the external electrode pad and the external terminal electrode.
Step (vii): a step of singulating the cured sealing body to which the external terminal electrode is connected to obtain a semiconductor device.

In the above steps (iv) to (vii), the adhesive sheet bonded to the cured sealing body supports the cured sealing body while protecting the circuit surface of the semiconductor chip in the cured sealing body, and each step Contribute to the improvement of

Although the singulated semiconductor device obtained through the step (vii) is mounted on a printed wiring board or the like, it is separated from the adhesive sheet before mounting.
The method for separating the semiconductor device from the pressure-sensitive adhesive sheet is not particularly limited, but the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is formed of a pressure-sensitive adhesive composition containing an energy ray-curable pressure-sensitive adhesive resin and a photopolymerization initiator. In the case where the semiconductor device is present, the irradiation with energy rays reduces the adhesive strength and facilitates separation of the semiconductor device.

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

<Mass average molecular weight (Mw)>
It measured under the following conditions using the gel permeation chromatograph apparatus (Tosoh Corp. make, a product name "HLC-8020"), and used the value measured in standard polystyrene conversion.
(Measurement condition)
・ Column: “TSK guard column HXL-L”, “TSK gel G2500 HXL”, “TSK gel G2000 HXL”, “TSK gel G1000 HXL” (all manufactured by Tosoh Corporation) • Column temperature: 40 ° C.
-Developing solvent: tetrahydrofuran-Flow rate: 1.0 mL / min

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

<Average particle size (D ₅₀ ) of thermally expandable particles, 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 apparatus (for example, product name “Mastersizer 3000” manufactured by Malvern Co., Ltd.).
Then, the particle diameter corresponding to 50% and 90% of the cumulative volume frequency calculated from the smaller particle diameter of the particle distribution is referred to as “average particle diameter (D ₅₀ ) of thermally expandable fine particles” and “thermally expandable particles, respectively. 90% particle diameter (D ₉₀ ) of

<Storage elastic modulus E ′ of thermally expandable base material layer (Y1-1)>
The formed thermally expandable base material layer (Y1-1) was made to have a size of 5 mm long × 30 mm wide × 200 μm thick, and the release material was removed to obtain a test sample.
Test start temperature 0 ° C, test end temperature 300 ° C, temperature rise rate 3 ° C / min, frequency 1 Hz, amplitude 20μm using a dynamic viscoelasticity measurement device (product made by TA Instruments, product name "DMAQ800") The storage elastic modulus E ′ of the test sample was measured at a predetermined temperature under the following conditions.

<Storage Shear Modulus G ′ of Pressure-Sensitive Adhesive Layers (X1) and (X2)>
The formed pressure-sensitive adhesive layers (X1) and (X2) were cut into a circle having a diameter of 8 mm, the release material was removed, and the layers having a thickness of 3 mm were used as test samples.
Using a visco-elasticity measuring device (manufactured by Anton Paar, device name “MCR 300”), torsional shear method under the conditions of test start temperature 0 ° C., test end temperature 300 ° C., temperature rising rate 3 ° C./min, frequency 1 Hz. The storage shear modulus G ′ of the test sample was measured at a given temperature by

<Probe Tack Value>
The base material to be measured was cut into a square of 10 mm on a side, and allowed to stand for 24 hours under an environment of 23 ° C. and 50% RH (relative humidity) as a test sample.
The probe tack value on the surface of the test sample is measured by using a tacking tester (product name: "NTS-4800" manufactured by Japan Specialty Instruments Co., Ltd.) under an environment of 23 ° C and 50% RH (relative humidity) according to JIS It measured based on Z0237: 1991.
Specifically, after bringing a 5 mm diameter stainless steel probe into contact with the surface of a test sample with a contact load of 0.98 N / cm ² for 1 second, the probe is subjected to the test sample at a speed of 10 mm / sec. The force required to move away from the surface was measured and the resulting value was taken as the probe tack value for the test sample.

<Measurement of adhesion of pressure-sensitive adhesive layer before heat treatment>
On a pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer formed on the release film, a 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) was laminated to form a pressure-sensitive adhesive sheet with a substrate.
Then, the release film is removed, and the adhesive surface of the exposed adhesive layer is attached to the adherend, stainless steel plate (SUS304 No. 360, polished), 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 tension rate of 300 mm / min by a 180 ° peeling method based on JIS Z 0237: 2000 under the same environment.

Production Example 1 (Synthesis of Urethane Prepolymer)
In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate is added to 100 parts by mass (solid content ratio) of a carbonate type diol having a mass average molecular weight of 1,000, and an equivalent ratio of hydroxyl group of carbonate type diol and isocyanate group of isophorone diisocyanate. Was added so as to be 1/1, and 160 parts by mass of toluene was further added, and the mixture was reacted at 80 ° C. for 6 hours or more until the isocyanate group concentration reached a theoretical amount while stirring under a nitrogen atmosphere.
Then, add a solution of 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) diluted in 30 parts by mass of toluene, and further add isocyanate groups at both ends at 80 ° C. until disappearance. The mixture was reacted for 6 hours to obtain a urethane prepolymer having a weight average molecular weight of 29,000.

Production Example 2 (Synthesis of Acrylic Urethane Resin)
In a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solids ratio) of the urethane prepolymer obtained in Production Example 1, 117 parts by mass of methyl methacrylate (MMA) (solids ratio), 2-hydroxyethyl methacrylate (2-HEMA) 5.) 5.1 parts by mass (solids ratio), 1 part by mass of 1-thioglycerol (solids ratio), and 50 parts by mass of toluene were added, and the temperature was raised to 105 ° C. while stirring.
Then, a solution obtained by further diluting 2.2 parts by mass (solid content ratio) of a radical initiator (product name “ABN-E”, product name: “ABN-E”) in a reaction vessel with 210 parts by mass of toluene is brought to 105 ° C. It dripped over 4 hours, maintaining it.
After completion of the dropwise addition, reaction was carried out at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin having a mass average molecular weight of 105,000.

The details of the adhesive resin, additives, thermally expandable particles, base material and release material used in the formation of each layer in the following examples are as follows.
<Adhesive resin>
Acrylic copolymer (i): having a structural unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio), Acrylic copolymer of 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. The acrylic copolymer of Mw 600,000 which has a structural unit derived from the raw material monomer which consists of 0 (mass ratio).
Acrylic copolymer (iii): consisting of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid (AAc) = 92.8 / 7.0 / 0.2 (mass ratio) An acrylic copolymer having a structural unit derived from a raw material monomer.
<Additives>
-Isocyanate crosslinking agent (i): Tosoh Co., Ltd. make, product name "Coronato L", solid content concentration: 75 mass%.
-Isocyanate crosslinking agent (ii): Tosoh Co., Ltd. make, product name "Coronato HX", solid content concentration: 75 mass%.
Photopolymerization initiator (i): manufactured by BASF, product name “IRGACURE 184”, 1-hydroxy-cyclohexyl-phenyl-ketone.
Tackifier (i): manufactured by Nippon Soda Co., Ltd., product name “GI-1000”, hydrogenated polybutadiene having hydroxyl groups at both ends.
<Thermally expandable particles>
Thermally expandable particles (i): product name "S2640" manufactured by Kureha Co., Ltd., expansion start temperature (t) = 208 ° C, average particle size (D ₅₀ ) = 24 μm, 90% particle size (D ₉₀ ) = 49 μm .
<Peeling material>
Heavy release film: product manufactured by Lintec Co., Ltd., product name “SP-PET 382150”, provided with a release agent layer formed from a silicone release agent on one side of a polyethylene terephthalate (PET) film, thickness: 38 μm.
Light release film: manufactured by Lintec Co., Ltd., product name “SP-PET 381031”, provided with a release agent layer formed from a silicone release agent on one side of a PET film, thickness: 38 μm.

Example 1
In the pressure-sensitive adhesive laminate 2b shown in FIG. 2 (b), a release material was further laminated on the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) and the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II). An adhesive laminate having a constitution was produced in the following procedure.

[1] Production of Pressure-Sensitive Adhesive Sheet (I) (1-1) Formation of First Pressure-Sensitive Adhesive Layer (X11) The above isocyanate is added to 100 parts by weight of the solid content of the above-mentioned acrylic copolymer (i) which is a tacky resin. 5.0 parts by mass (solid content ratio) of a crosslinking agent (i) was mixed, diluted with toluene, and stirred uniformly to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass .
Then, the pressure-sensitive adhesive composition is applied to the surface of the release agent layer of the heavy release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to form a non-thermally expandable 5 μm thick film. The 1st adhesive layer (X11) which is an adhesive layer was formed.
The storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11) at 23 ° C. was 2.5 × 10 ⁵ Pa.
Moreover, the adhesive force of the 1st adhesive layer (X11) measured based on the said method was 0.3 N / 25 mm.

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

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

In addition, as a sample which measures the physical-property value of a thermally expandable base material layer (Y1-1), the said resin composition is apply | coated on the surface of the release agent layer of the said light release film, a coating film is formed, The film was dried at 100 ° C. for 120 seconds to form a 50 μm thick thermally expandable base layer (Y1-1) in the same manner.
Then, based on the above measurement method, the storage elastic modulus and the probe tack value at each temperature of the thermally expandable base material layer (Y1-1) were measured. The measurement results were as follows.
Storage elastic modulus E ′ (23) at 23 ° C. = 2.0 × 10 ⁸ Pa
Storage elastic modulus E '(100) at 100 ° C. = 3.0 × 10 ⁶ Pa
Storage elastic modulus E ′ (208) at 208 ° C. = 5.0 × 10 ⁵ Pa
· Probe tack value = 0 mN / 5 mmφ

(1-4) Lamination of Each Layer The non-heat-expandable substrate layer (Y1-2) of the substrate (Y1) produced in the above (1-3) and the second adhesive formed in the above (1-2) The layer (X12) was laminated, and the thermally expandable base material layer (Y1-1) and the second pressure-sensitive adhesive layer (X12) formed in the above (1-2) were laminated.
And light release film / second pressure-sensitive adhesive layer (X12) / non-thermally expandable substrate layer (Y1-2) / thermally-expandable substrate layer (Y1-1) / first pressure-sensitive adhesive layer (X11) / weight A pressure-sensitive adhesive sheet (I) was prepared by laminating a release film in this order.

[2] Production of Pressure-Sensitive Adhesive Sheet (II) (2-1) Formation of Pressure-Sensitive Adhesive Layer (X2) The isocyanate-based crosslinking is performed on 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (iii) which is a pressure-sensitive resin. Agent (ii) 8.75 parts by mass (solid content ratio) and the tackifier (i) 12.5 parts by mass, diluted with methyl ethyl ketone, uniformly stirred, solid content concentration (active ingredient Concentration) A pressure-sensitive adhesive composition of 30% by mass was prepared.
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, the coating film is dried at 90 ° C. for 90 seconds, and further dried at 115 ° C. for 90 seconds. And a 50 .mu.m thick adhesive layer (X2) was formed.
The storage shear modulus G ′ (23) of the pressure-sensitive adhesive layer (X2) at 23 ° C. was 2.36 × 10 ⁵ Pa.
Moreover, the adhesive force of the adhesive layer (X2) measured based on the said method was 1.2 N / 25 mm.

(2-2) Lamination of Each Layer A 50-μm-thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”, a probe, which is a non-thermally expandable substrate, is used as a substrate (Y2) Tack value: 0 mN / 5 mmφ) was used.
Then, the PET film used as the substrate (Y2) and the pressure-sensitive adhesive layer (X2) formed in the above (2-1) are laminated, and the substrate (Y2) / pressure-sensitive adhesive layer (X2) / heavy peeling A pressure-sensitive adhesive sheet (II) was prepared by laminating the films in this order.

[3] Production of Adhesive Laminate The first pressure-sensitive adhesive layer (X11) obtained by removing the heavy release film of the pressure-sensitive adhesive sheet (I) produced in the above [1] and exposing it, and the base material of the pressure-sensitive adhesive sheet (II) (Y2) was laminated to obtain an adhesive laminate.

The pressure-sensitive 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 substrate (Y2) of the pressure-sensitive adhesive sheet (II) before heat treatment. The peeling force (F ₀ ) and the peeling force (F ₁ ) at the time of peeling at the interface P by heat treatment were measured based on the following method.
As a result, peel force (F ₀ ) = 200 mN / 25 mm, peel force (F ₁ ) = 0 mN / 25 mm, and the ratio of peel force (F ₁ ) to peel force (F ₀ ) [(F ₁ ) / (F ₁ ) ₀ )] was 0.

<Measurement of peeling force (F ₀ )>
The prepared adhesive laminate is allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and then the heavy release film of the adhesive sheet (II) of the adhesive laminate is removed and exposed. The pressure-sensitive adhesive layer (X2) was attached to a stainless steel plate (SUS 304, polished No. 360).
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 (Orientech Co., Ltd., product name "Tensilon UTM-4-100").
Also, the upper chuck of the universal tensile tester is such that it peels 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 substrate (Y2) of the pressure-sensitive adhesive sheet (II). Fixed the adhesive sheet (I) of the adhesive laminate.
Then, under the same environment as described above, the peel force measured when peeled at the interface P at a tensile speed of 300 mm / min by 180 ° peel-off method based on JIS Z 0237: 2000 is referred to as “Peel force (F ₀ ) ".

<Measurement of peeling force (F ₁ )>
The heavy release film of the adhesive sheet (II) of the produced adhesive laminate was removed, and the exposed adhesive layer (X2) was attached to a stainless steel plate (SUS 304, polished No. 360).
Then, the stainless steel plate and the adhesive laminate were heated at 240 ° C. for 3 minutes to expand the thermally expandable particles in the thermally expandable base material layer (Y1-2) of the adhesive laminate.
Thereafter, the measurement is performed in the same manner as the measurement of the peel force (F ₀ ) described above, and under the above conditions, the first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) The peeling force measured when peeling at the interface P was taken as "peeling force (F ₁ )".
In the measurement of peeling force (F ₁ ), when trying to fix the adhesive sheet (I) of the adhesive laminate with the upper chuck of the universal tensile tester, the adhesive sheet (I) is completely separated at the interface P When it can not be fixed, the measurement is ended, and the peeling force (F ₁ ) at that time is set to “0 mN / 25 mm”.

Example 2
According to the following procedure, a cured and sealed article with an adhesive sheet was produced.
(1) Mounting of semiconductor chip The light-peelable film of the adhesive laminate prepared in Example 1 is removed, and the adhesive surface of the second adhesive layer (X12) of the adhesive sheet (I) exposed is a support I affixed it.
Then, the heavy release film of the adhesive laminate is removed, and on the adhesive surface of the adhesive layer (X2) of the adhesive sheet (II) exposed, nine semiconductor chips (each chip size is 6.4 mm A chip of 6.4 mm in thickness and 200 μm in chip thickness (# 2000) was placed at necessary intervals such that the circuit surface of each semiconductor chip was in contact with the adhesive surface.

(2) Formation of Cured Sealed Body The nine semiconductor chips and the adhesive surface of the pressure-sensitive adhesive layer (X2) at least at the periphery of the semiconductor chip are covered with a sealing resin film, and a vacuum heating and pressure laminator The sealing resin film was cured using (7024HP5 manufactured by ROHM and HAAS) to prepare a cured sealing body.
In addition, sealing conditions are as follows.
Preheating temperature: 100 ° C for both table and diaphragm
Vacuum suction: 60 seconds Dynamic press mode: 30 seconds Static press mode: 10 seconds Sealing temperature: 180 ° C. × 60 minutes

(3) Separation at Interface P After the above (2), the adhesive laminate was subjected to a heat treatment at 240 ° C. for 3 minutes, which is equal to or higher than the expansion start temperature (208 ° C.) of the thermally expandable particles. And it was able to separate easily collectively collectively in the interface P of the 1st adhesive layer (X11) of adhesive sheet (I), and the base material (Y2) of adhesive sheet (II).
Then, after separation, a cured and sealed product with a pressure-sensitive adhesive sheet is obtained, in which the cured and sealed body is laminated on the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II).

1a, 1b, 1c, 1d, 2 Adhesive laminate (I) Pressure-sensitive adhesive sheet (X1) Pressure-sensitive adhesive layer (X11) First pressure-sensitive adhesive layer (X12) Second pressure-sensitive adhesive layer (Y1) Base material (Y1-1) Thermally expandable substrate layer (Y1-2) Non-thermally expandable substrate layer (II) Pressure-sensitive adhesive sheet (X2) Pressure-sensitive adhesive layer (Y2) Substrate 50 Support 60 Process inspection object P Interface

Claims

A thermally expandable pressure-sensitive adhesive sheet (I) comprising a substrate (Y1) and a pressure-sensitive adhesive layer (X1), and including thermally expandable particles having an expansion start temperature (t) of 60 to 270 ° C. in any layer; ,
And a pressure-sensitive adhesive sheet (II) having a substrate (Y2) and a pressure-sensitive adhesive layer (X2) on one surface side of the substrate (Y2),
A pressure-sensitive adhesive laminate (I) and a substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated.
The adhesive laminated body isolate | separated in the interface P of adhesive sheet (I) and the base material (Y2) of adhesive sheet (II) by heat processing at temperature more than expansion | swelling start temperature (t).
The pressure-sensitive adhesive laminate according to claim 1, wherein a peeling force (F 1 ) at the time of separation at the interface P is 0 to 2000 mN / 25 mm by the heat treatment.
The adhesive laminate according to claim 1 or 2, wherein the peeling force (F 0 ) at the time of separation at the interface P before the heat treatment is 100 mN / 25 mm or more and larger than the peeling force (F 1 ). body.
The pressure-sensitive adhesive laminate according to claim 3, wherein a ratio of the peeling force (F 1 ) to the peeling force (F 0 ) [(F 1 ) / (F 0 )] is 0 to 0.9.
The pressure-sensitive adhesive laminate according to any one of claims 1 to 4, wherein a probe tack value on the surface of the substrate (Y1) is less than 50 mN / 5 mmφ.
The adhesive according to any one of claims 1 to 5, wherein the substrate (Y1) of the pressure-sensitive adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing the thermally expandable particles. Stack.
The thermally expandable substrate layer (Y1-1) of the substrate (Y1) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated to each other, Adhesive laminate as described.
The pressure-sensitive adhesive sheet (I) has a structure in which the base material (Y1) is held between the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12),
The pressure-sensitive adhesive laminate according to claim 6 or 7, wherein 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 adhesive laminate according to claim 8, wherein the adhesive strength of the second adhesive layer (X12) is higher than the adhesive strength of the first adhesive layer (X11).
The substrate (Y1) has a thermally expandable substrate layer (Y1-1) on one surface side and a non-thermally expandable substrate layer (Y1-2) on the other surface side. 11. The pressure-sensitive adhesive laminate according to any one of to 9.
The first pressure-sensitive adhesive layer (X11) is laminated on the surface side of the thermally expandable base material layer (Y1-1),
The second pressure-sensitive adhesive layer (X12) is laminated on the surface side of the non-thermally expandable substrate layer (Y1-2),
The adhesive laminate according to claim 10.
The first pressure-sensitive adhesive layer (X11), which is a heat-expandable pressure-sensitive adhesive layer containing heat-expandable particles, and the non-heat-expandable pressure-sensitive adhesive layer respectively on both sides of the substrate (Y1) Having a second adhesive layer (X12),
The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) are directly laminated,
The adhesive laminate according to any one of claims 1 to 5.
The pressure-sensitive adhesive laminate according to claim 12, wherein the content of the thermally expandable particles in the second pressure-sensitive adhesive layer (X12) which is a non-thermally expandable pressure-sensitive adhesive layer is less than 1% by mass.
The usage method of the adhesive laminated body which has following process (1)-(3).
Step (1): A processing inspection object is fixed to a support via the adhesive laminate according to any one of claims 1 to 13, and the support, the adhesive laminate, and the above Process of laminating processing inspection objects in this order.
Step (2): a step of processing and / or inspecting the object to be processed and inspected.
Step (3): Separation at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) Process.
The step (1) adheres the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate and the support, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate. The usage method of the adhesive laminated body of Claim 14 which is a process of sticking (X1) and the said process inspection target object.
A process (1) sticks the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the support, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (II) of the pressure-sensitive adhesive laminate. The usage method of the adhesive laminated body of Claim 14 which is a process of sticking (X2) and the said process inspection target object.
A method of manufacturing a semiconductor device using the adhesive laminate according to any one of claims 1 to 13, which comprises the following steps (i) to (iii).
Step (i): The pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the pressure-sensitive adhesive surface (X2) of the pressure-sensitive adhesive sheet (II) And attaching the semiconductor chip to a part of the other adhesive surface.
Step (ii): covering the semiconductor chip and the adhesive surface of the pressure-sensitive adhesive layer (X1) or (X2) of at least the periphery of the semiconductor chip with a sealing material, and curing the sealing material, A step of obtaining a cured sealing body in which the semiconductor chip is sealed in a curing sealing material.
Step (iii): Separation at the interface P between the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the substrate (Y2) of the pressure-sensitive adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) And a step of obtaining a cured seal with a pressure-sensitive adhesive sheet, wherein the cured seal is laminated on the pressure-sensitive adhesive sheet (I) or (II).
In the step (i), the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) and the support are attached, and a semiconductor is formed on a portion of the pressure-sensitive adhesive surface (X1) of the pressure-sensitive adhesive sheet (I) The method of manufacturing a semiconductor device according to claim 17, wherein a chip is mounted.
In the step (i), the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the support are attached, and a part of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X2) of the pressure-sensitive adhesive sheet (II) is a semiconductor The method of manufacturing a semiconductor device according to claim 17, wherein a chip is mounted.