WO2019131408A1 - Adhesive layered body, method for manufacturing object to be processed with resin film, and method for manufacturing hardened sealing body with hardened resin film - Google Patents

Abstract

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

Description

Adhesive laminate, method for producing object to be processed with resin film, and method for producing cured sealing material with cured resin film

The present invention relates to a pressure-sensitive adhesive laminate, a method for producing an object to be processed with a resin film using the pressure-sensitive adhesive laminate, and a method for producing a cured and sealed film with a cured resin film.

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. May be
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 temporarily 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. ing.
This heat-peelable pressure-sensitive adhesive sheet adjusts the maximum particle diameter 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 process of processing using a pressure-sensitive adhesive sheet as described in Patent Document 1, an object to be processed (hereinafter, also referred to as a "processing object") is temporarily fixed using the pressure-sensitive adhesive sheet. After processing, the object to be processed is separated from the adhesive sheet.
By the way, especially in the manufacture of electronic components, there are many cases in which a plurality of processing steps are performed.
When a plurality of processing steps are required for the processing object, the processing object after processing is separated from the pressure-sensitive adhesive sheet and then attached again to a new pressure-sensitive adhesive sheet, and then processing of the next step May be served.

However, the operation of attaching the object to be processed to a new pressure-sensitive adhesive sheet in each process is complicated and leads to a decrease in the productivity of the product.
For example, a cured resin is used to protect the back side of a processing object such as a semiconductor chip attached to a pressure sensitive adhesive sheet and subjected to predetermined processing, or to provide a die bonding function. A film may be formed. From such a purpose, a resin film forming sheet having a curable resin layer may be used.
In this case, after separating the object to be processed from the adhesive sheet, a sheet for resin film formation having a curable resin layer separately prepared is attached to the object to be processed, and cured on the curable resin layer to cure the resin film. It is common to form
That is, in order to obtain a processing object having a cured resin film, two adhesive sheets for performing predetermined processing and a resin film forming sheet for forming a cured resin film are attached as described above. Pasting work was necessary.

According to the present invention, an object to be processed can be fixed to a support and predetermined processing can be carried out, and after processing, the support can be easily separated from the support collectively with a slight force, and the support It aims at providing an adhesive layered product which can obtain a processing object with a resin film by separating from.

The present inventors have a thermally expandable pressure-sensitive adhesive sheet (I) having a substrate and a pressure-sensitive adhesive layer, and including a layer containing thermally expandable particles in any layer, a substrate and a curable resin layer An adhesive laminate comprising the resin film-forming sheet (II) and the adhesive sheet (I) and the base material of the resin film-forming sheet (II) being directly laminated can solve the above-mentioned problems. Found out.

That is, the present invention relates to the following [1] to [13].
[1] A thermally expandable pressure-sensitive adhesive sheet (I) which has a substrate (Y1) and a pressure-sensitive adhesive layer (X1) and which contains thermally expandable particles in any layer,
And a sheet (II) for forming a resin film having a substrate (Y2) and a curable resin layer (Z2),
The pressure-sensitive adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation are directly laminated,
An adhesive laminate used to fix an object to be processed to a support when predetermined processing is performed,
The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support,
The surface of the curable resin layer (Z2) of the sheet (II) for resin film formation is a surface to which the object to be processed is attached,
Separating at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation by heat treatment at a temperature higher than the thermal expansion start temperature (t) of the thermally expandable particles Is an adhesive laminate.
[2] The adhesive laminate according to the above [1], wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270 ° C.
[3] The adhesion according to the above [1] or [2], wherein the substrate (Y1) contained in the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing the thermally expandable particles Sex stacks.
[4] In the above-mentioned [3], the substrate (Y1) of the pressure-sensitive adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2) Adhesive laminate as described.
[5] The thermally expandable base material layer (Y1-1) of the base material (Y1) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are directly laminated. The adhesive laminated body as described in said [3] or [4].
[6] The pressure-sensitive adhesive sheet (I) has a configuration 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 first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the sheet (II) for forming a resin film are directly laminated,
The pressure-sensitive adhesive laminate according to any one of the above [3] to [5], wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support.
[7] The pressure-sensitive adhesive sheet (I) has a configuration 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 first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles,
The second pressure-sensitive adhesive layer (X12) is a non-heat-expandable pressure-sensitive adhesive layer,
The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the sheet (II) for forming a resin film are directly laminated,
The adhesive laminate according to the above [1] or [2], wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support.
[8] The adhesive according to any one of the above [1] to [7], wherein the surface of the substrate (Y2) on which the pressure-sensitive adhesive sheet (I) is laminated is the surface subjected to the peeling treatment. Stack.
[9] The curable resin layer (Z2) is a layer formed of a curable composition (z) containing a polymer component (A) and a curable component (B), [1] to [8] above The adhesive laminate according to any one of the above.
[10] A method for producing an object to be processed with a resin film, using the adhesive laminate according to any one of the above [1] to [9],
A method for producing a processing object having a resin film, comprising the following steps (α-1) to (α-3):
Step (α-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) Step / Step (α-2) of placing or sticking the object to be processed on the surface of Z2): Step / step (α-3) of performing predetermined processing on the object: heat of the thermally expandable particles A process of obtaining an object to be processed with a resin film by separating at the interface P between the adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation by heating at expansion start temperature (t) or higher [11] The method for producing an object to be processed with a resin film according to the above [10], wherein the curable resin layer (Z2) is cured in the step (α-2) to form a cured resin film.
[12] The method for producing an object to be processed with a resin film according to the above [10], comprising the following step (α-2 ′) after the step (α-2) and before the step (α-3).
Step (α-2 ′): a step of curing the curable resin layer (Z2) to form a cured resin film.
[13] A method for producing a cured sealing film with a cured resin film, using the adhesive laminate according to any one of the above [1] to [9],
A method for producing a cured molded article with a cured resin film, comprising the following steps (β-1) to (β-3):
Step (β-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) Step / Step (β-2) of placing a semiconductor chip on Z2): the semiconductor chip is covered with a sealing material, and the sealing material is cured to cure and seal the semiconductor chip And curing the curable resin layer (Z2) to form a cured resin film / step (β-3): adhesion at the heat expansion start temperature (t) or more of the thermally expandable particles A step of separating at the interface P between the sheet (I) and the base material (Y2) of the sheet (II) for resin film formation to obtain a cured resin film-attached cured sealing body

The adhesive laminate of the present invention can fix the object to be processed to a support and carry out predetermined processing, and can be easily separated from the support collectively with a slight force after processing. And by separating from a support body, a processing object with a resin film can be obtained.

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.

In the present specification, it is determined as follows whether the target layer is a "non-thermally expandable layer".
The target layer is heat-treated for 3 minutes at the expansion start temperature (t) of the thermally expandable particles contained in the layer containing the thermally expandable particles. When 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.
In the present specification, the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC), and specifically, a value measured based on the method described in the examples. It is.
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.
In the present specification, the lower limit value and the upper limit value described stepwise with respect to a preferable numerical range (for example, range such as content) can be combined independently. 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]
A pressure-sensitive adhesive laminate (I) according to the present invention comprises a substrate (Y1) and a pressure-sensitive adhesive layer (X1), and the heat-expandable pressure-sensitive adhesive sheet (I) comprising heat-expandable particles in any layer; A sheet (II) for forming a resin film having (Y2) and a curable resin layer (Z2), and the adhesive sheet (I) and the base material (Y2) of the sheet (II) for forming a resin film are directly It is used to fix the object to be processed on a support when it is laminated and subjected to predetermined processing.

In the pressure-sensitive adhesive laminate of the present invention, the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to a support.
That is, the pressure-sensitive adhesive sheet (I) has at least one pressure-sensitive adhesive layer (X1), and the surface of one pressure-sensitive adhesive layer (X1) is attached to the surface of the support.
In addition, when adhesive sheet (I) has 1st adhesive layer (X11) and 2nd adhesive layer (X12) on both surfaces of base material (Y1), the surface of 2nd adhesive layer (X12) is The surface to be attached to the support and the surface of the first pressure-sensitive adhesive layer (X11) is to be attached to the substrate (Y2) of the sheet (II) for forming a resin film.

Moreover, the surface of the curable resin layer (Z2) of the sheet (II) for resin film formation is a surface to which an object to be processed is attached. The curable resin layer (Z2) is a curable resin layer, and can be cured to form a cured resin film. The curing treatment may be performed in parallel with the predetermined processing, or may be performed after the predetermined processing.

And the adhesive laminated body of this invention is the base material (A) of adhesive sheet (I) and sheet | seat (II) for resin film formation by heat processing at the temperature more than expansion start temperature (t) of thermally expansible particle It is separable at the interface P with Y2). In the following description, the heat treatment is also referred to as “separation heat treatment”.
Therefore, after the processing object is fixed to a support using the adhesive laminate of the present invention, and the processing object is subjected to predetermined processing, processing is performed by separating at the interface P by the heat treatment. It is possible to obtain an object to be processed with a resin film, in which the resin film-forming sheet (II) is laminated on the object.
Here, the processing object with a resin film may be a processing object with a cured resin film formed by curing of the curable resin layer (Z2), and the curable resin layer (Z2) is not cured. It may be a processing object with a curable resin film.
In the following description, “resin film” means “cured resin film” formed by curing of the curable resin layer (Z2), and “curable” where the curable resin layer (Z2) is uncured. "Both resin film" is shown.

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

<Adhesive laminate of the first aspect>
As an adhesive laminated body of the 1st aspect of this invention, adhesive laminated body 1a, 1b shown, for example to FIG. 1 (a), (b) is mentioned.
The adhesive laminates 1a and 1b are a resin film-forming sheet having a pressure-sensitive adhesive sheet (I) having a substrate (Y1) and a pressure-sensitive adhesive layer (X1), and a substrate (Y2) and a curable resin layer (Z2). And (II), and has a configuration in which the base (Y1) of the pressure-sensitive adhesive sheet (I) and the base (Y2) of the sheet (II) for forming a resin film are directly laminated.

In the pressure-sensitive adhesive laminate of the present invention, any layer of the pressure-sensitive adhesive sheet (I) is a layer containing thermally expandable particles so that separation can be performed at the interface P by the separation heat treatment.
In the pressure-sensitive adhesive laminate of the present invention, the thermally expandable particles are expanded by the heat treatment for separation, and irregularities are generated on the surface of the layer containing the thermally expandable particles. Thereby, the contact area of adhesive sheet (I) and the base material (Y2) of sheet | seat (II) for resin film formation reduces.
As a result, an object to be processed is attached on the surface of the curable resin layer (Z2) of the sheet (II) for forming a resin film, and after predetermined processing, the adhesive sheet (I) and the sheet for forming a resin film ( By separating at the interface P with the substrate (Y2) of II), it is possible to obtain the object to be processed attached to the sheet (II) for forming a resin film.

Therefore, while being able to fix a process target object to a support body via the said adhesive laminated body, and implementing predetermined processing, the adhesive laminated body of this invention is said processing after implementing predetermined processing. The object can be easily separated from the support at the interface P collectively with a slight force. After separation from the support, it is possible to obtain an object to be processed with a resin film-forming sheet.
Therefore, using the adhesive laminate of the present invention has, for example, the following advantages.
-It is not necessary to perform the operation | work which affixes the sheet | seat for resin film formation to the process target after isolation | separation in a next process.
· Even when the object to be processed is thinned and fragile, the sheet for forming a resin film is attached to the object to be processed, so that the support performance is imparted and the handleability such as transport to the next process is good It can be.

In the first embodiment of the present invention, the substrate (Y1) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles as in the adhesive laminates 1a and 1b shown in FIG. Is preferred.
In addition, a base material (Y1) is a single layer structure which has only a thermally expandable base material layer (Y1-1) containing thermally expandable particles like the adhesive laminated body 1a shown to Fig.1 (a). May be
In addition, as the adhesive laminate 1b shown in FIG. 1 (b), the substrate (Y1) is a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2) And may have a multi-layer configuration.

In the adhesive laminate 1a shown in FIG. 1A, the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) are expanded by the heat treatment for separation, Irregularities occur on the surface of the substrate (Y1) on the sheet (II) side for resin film formation, and the contact area between the substrate (Y1) and the substrate (Y2) for the resin film formation sheet (II) decreases. .
On the other hand, since the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate 1a is attached to a support, unevenness is hard to be formed on the surface of the base (Y1) on the pressure-sensitive adhesive layer (X1) side. Thereby, an unevenness | corrugation can be efficiently formed in the surface of the base material (Y1) in contact with sheet | seat (II) for resin film formation.
As a result, the adhesive laminate 1a is easily collectively at a slight force at the interface P between the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the sheet (II) for resin film formation. Can be separated.
Incidentally, by forming the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive laminate 1a from a pressure-sensitive adhesive composition which increases the adhesion to the support, separation can be more easily performed at the interface P. It is also possible to design.

In the adhesive laminate 1b shown in FIG. 1 (b), the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) are expanded by the separation heat treatment. Surface irregularities on the resin film forming sheet (II) side of the base material (Y1), and the contact area between the base material (Y1) and the base material (Y2) of the resin film forming sheet (II) is Decrease.
On the other hand, the surface of the non-thermally expandable substrate layer (Y1-2) constituting the substrate (Y1) on the pressure-sensitive adhesive layer (X1) side of the substrate (Y1) because the degree of expansion by heat treatment is small. It is difficult to form irregularities on the surface. Thereby, an unevenness | corrugation can be efficiently formed in the surface at the side of the sheet | seat (II) for resin film formation of a base material (Y1).
As a result, the pressure-sensitive adhesive laminate 1b is easily collectively at a slight force at the interface P between the substrate (Y1) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the sheet (II) for resin film formation. Can be separated.

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

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

<Adhesive laminate of the second aspect>
As an adhesive laminated body of the 2nd aspect of this invention, adhesive laminated body 1c, 1d shown, for example to FIG. 2 (a), (b) is mentioned.
The adhesive laminates 1c and 1d shown in FIG. 2 have a configuration in which the adhesive sheet (I) has the substrate (Y1) sandwiched between the first adhesive layer (X11) and the second adhesive layer (X12). The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the sheet (II) for forming a resin film are directly laminated.
In the adhesive laminates 1c and 1d, the surface of the second pressure-sensitive adhesive layer (X12) is a surface to be attached to the support.

In the second embodiment of the present invention, as in the adhesive laminates 1c and 1d shown in FIG. 2, the substrate (Y1) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles. Is preferred.
In addition, a base material (Y1) is a single layer structure which has only a thermally expandable base material layer (Y1-1) containing thermally expandable particles like the adhesive laminated body 1c shown to Fig.2 (a). May be In addition, as the adhesive laminate 1d shown in FIG. 2 (b), the substrate (Y1) is a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2) And may have a multi-layer configuration.
When the substrate (Y1) has a multilayer structure having a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2), the thermally expandable substrate layer Preferably, (Y1-1) is disposed on the resin film-forming sheet (II) side, and the non-thermally expandable substrate layer (Y1-2) is disposed on the second pressure-sensitive adhesive layer (X12) side.

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 for separation, and (1) Irregularities occur on the surface of the base material (Y1) on the pressure-sensitive adhesive layer (X11) side. Then, the first pressure-sensitive adhesive layer (X11) is also pushed up by the unevenness generated on the surface of the substrate (Y1), and the unevenness is also observed on the surface of the first pressure-sensitive adhesive layer (X11) on the resin film forming sheet (II) side. It is formed. Thereby, the contact area of a 1st adhesive layer (X11) and the base material (Y2) of sheet | seat (II) for resin film formation reduces.
On the other hand, since the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive laminate 1c is attached to the support, the surface of the base (Y1) on the second pressure-sensitive adhesive layer (X12) side has irregularities. It is difficult to form. Therefore, unevenness is efficiently formed on the surface of the substrate (Y1) on the side of the first adhesive layer (X11), and unevenness is easily formed also on the surface of the first pressure-sensitive adhesive layer (X11).
As a result, the adhesive laminate 1c is batched with a slight force at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the sheet (II) for resin film formation. And can be easily separated.
Incidentally, by forming the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive laminate 1c from a pressure-sensitive adhesive composition that increases the adhesion to the support, separation can be more easily performed at the interface P. It is also possible to design.

In the adhesive laminate 1d shown in FIG. 2 (b), the thermally expandable particles contained in the thermally expandable substrate layer (Y1-1) constituting the substrate (Y1) are expanded by the separation heat treatment. As a result, the surface of the base (Y1) on the side of the first pressure-sensitive adhesive layer (X11) is roughened. Then, the first pressure-sensitive adhesive layer (X11) is also pushed up by the unevenness generated on the surface of the substrate (Y1), and the unevenness is also observed on the surface of the first pressure-sensitive adhesive layer (X11) on the sheet (II) for resin film formation It is formed. Thereby, the contact area of a 1st adhesive layer (X11) and the base material (Y2) of sheet | seat (II) for resin film formation reduces.
On the other hand, the non-heat-expandable substrate layer (Y1-2) constituting the substrate (Y1) has a small degree of expansion due to heat treatment, so the second pressure-sensitive adhesive layer (X12) side of the substrate (Y1) Irregularities are difficult to be formed on the surface of. Thereby, an unevenness | corrugation can be efficiently formed in the surface at the side of the 1st adhesive layer (X11) of a base material (Y1).
As a result, the adhesive laminate 1d is easily collectively at a slight force at the interface P between the substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the sheet (II) for resin film formation. Can be separated.

Here, also in the second aspect of the present invention, the adhesive laminates 1c and 1d are adhesive sheets (I It is preferable that the thermally expandable base material layer (Y1-1) and the first pressure-sensitive adhesive layer (X11) of the base material (Y1) possessed by) be directly laminated. In this case, it is more preferable that the first pressure-sensitive adhesive layer (X11) and the base material (Y2) of the resin film-forming sheet (II) be further directly laminated.

<Adhesive laminate of third aspect>
The adhesive laminates 1a and 1b according to the first aspect of the present invention and the adhesive laminates 1c and 1d according to the second aspect of the present invention each have thermal expansion as one of the layers constituting the substrate (Y1). A layer containing sexual particles is included.
On the other hand, as the adhesive laminate of the third aspect of the present invention, a thermally expandable pressure-sensitive adhesive layer containing the thermally expandable particles is provided on the surface on the interface P side of the substrate (Y1) of the pressure-sensitive adhesive sheet (I). The non-heat-expandable pressure-sensitive adhesive layer may be provided on the other surface of the substrate (Y1).
In such an embodiment, for example, as in the pressure-sensitive adhesive laminate 2 shown in FIG. 3, the pressure-sensitive adhesive sheet (I) comprises a substrate (the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12)) The first pressure-sensitive adhesive layer (X11) is a thermally expandable pressure-sensitive adhesive layer containing thermally expandable particles, and the second pressure-sensitive adhesive layer (X12) is non-thermally expandable. It is an adhesive layer, and what has the structure which the 1st adhesive layer (X11) of adhesive sheet (I) and the base material (Y2) of sheet | seat (II) for resin film formation laminated | stacked directly is mentioned.
In the above-mentioned composition like adhesive layered product 2, the surface of the 2nd adhesive layer (X12) is a field stuck with a support.
In the above-mentioned composition like adhesive layered product 2, it is preferred that a substrate (Y1) is a non-heat-expansible substrate.

In the pressure-sensitive adhesive laminate 2 shown in FIG. 3, unevenness is generated on the surface of the thermally expandable pressure-sensitive adhesive layer which is the first pressure-sensitive adhesive layer (X11) by the heat treatment for separation, and the first pressure-sensitive adhesive layer (X11) The contact area of the resin film forming sheet (II) with the substrate (Y2) is reduced.
On the other hand, since the base material (Y1) which is a non-heat-expansible base material is laminated in the surface by the side of the base material (Y1) of the 1st adhesive layer (X11), it is hard to produce unevenness. Therefore, asperities are efficiently formed on the surface of the first pressure-sensitive adhesive layer (X11) on the resin film-forming sheet (II) side.
As a result, the pressure-sensitive adhesive laminate 2 is collectively attached 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 sheet (II) for resin film formation. And can be easily separated.

<Configuration of adhesive laminate having a release material>
In the pressure-sensitive adhesive laminate of one embodiment of the present invention, the surface of the pressure-sensitive adhesive layer (X1) to which the support is attached and the surface of the curable resin layer (Z2) to which the object to be processed is attached It is good also as composition which laminated materials.
For example, in the adhesive laminates 1a and 1b shown in FIGS. 1 (a) and 1 (b), both adhesive surfaces of the adhesive layer (X1) and the curable resin layer (Z2) are subjected to peeling treatment on both surfaces It is good also as composition which wound the thing which laminated the exfoliation material in roll shape. The adhesive laminates 1c and 1d shown in FIGS. 2 (a) and 2 (b) and the adhesive laminate 2 shown in FIG. 3 may be similarly wound in a roll.

[Various physical properties of adhesive laminate]
The adhesive laminate of one aspect of the present invention is a substrate of an adhesive sheet (I) and a resin film-forming sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) of the thermally expandable particles. At the interface P with (Y2), it can be easily separated at once with a slight force.
Here, in the adhesive laminate of one embodiment of the present invention, the peeling force (F ₁ ) at the time of separation at the interface P by heat treatment at a temperature higher than the expansion start temperature (t) of the thermally expandable particles Usually, it is 0 to 2000 mN / 25 mm, preferably 0 to 1000 mN / 25 mm, more preferably 0 to 150 mN / 25 mm, further 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.

In addition, from the viewpoint of sufficiently fixing the object to be processed before heat treatment so as not to adversely affect the processing operation, the base material (Y2) of the adhesive sheet (I) and the sheet (II) for forming a resin film It is preferable that the interlaminar adhesion with the above be high.
From the above viewpoint, in the adhesive laminate of one embodiment of the present invention, the peeling force (F ₀ ) at the time of separation at the interface P before heat treatment is preferably 100 mN / 25 mm or more, more preferably 130 mN. / 25 mm or more, more preferably 160 mN / 25 mm or more, and preferably 50000 mN / 25 mm or less.

In the adhesive laminate of one embodiment of the present invention, the peeling force (F ₀ ) is larger than the peeling 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.) The adhesive strength of (a) is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, still more preferably 0. 5 to 4.0 N / 25 mm.
When adhesive sheet (I) has a 1st adhesive layer (X11) and a 2nd adhesive layer (X12), the adhesive force of a 1st adhesive layer (X11) and a 2nd adhesive layer (X12) is respectively Although it is preferable that it is the said range, from a viewpoint of improving adhesiveness with a support body, and making it possible to separate easily collectively at the interface P, a 2nd adhesive layer (X12) stuck with a support body The adhesion is more preferably higher than the adhesion of the first pressure-sensitive adhesive layer (X11).

In addition, in the adhesive laminate of one aspect of the present invention, the surface of the curable resin layer (Z2) of the resin film-forming sheet (II) from the viewpoint of making the adhesion with the object to be attached better. Is preferably adhesive.
Specifically, the adhesive strength of the curable resin layer (Z2) of the resin film-forming sheet (II) at room temperature (23 ° C.) is preferably 0.01 to 5 N / 25 mm, more preferably 0. It is preferably 5 to 4 N / 25 mm, more preferably 0.1 to 3 N / 25 mm.

In the present specification, the adhesive force of the pressure-sensitive adhesive layer (X1) (the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12)) and the curable resin layer (Z2) is given in Examples. It means the value measured by the method described.

The base material (Y1) which adhesive sheet (I) has, and the base material (Y2) which sheet | seat (II) for resin film formation 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 sheet (II) for resin film formation is each independently 50 mN / h. It is less than 5 mmφ, 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 adhesive sheet (I) of the adhesive laminate of the present invention has a substrate (Y1) and an adhesive layer (X1), and the heat treatment for separation is used as a base of the resin film forming sheet (II) ( It is a thermally expandable pressure-sensitive adhesive sheet containing thermally expandable particles in any layer so as to be separated at the interface with Y2).
In one embodiment of the present invention, the thermal expansion onset temperature (t) of the thermally expandable particles is preferably 60 to 270 ° C.

As the pressure-sensitive adhesive sheet (I) used in one aspect of the present invention, the following 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.
Pressure-sensitive adhesive sheet (I), wherein the substrate (Y1) is a non-thermally expandable substrate.
Hereinafter, the adhesive sheet (I) of 1st aspect and 2nd aspect used by 1 aspect of this invention is demonstrated.

<Pressure-sensitive 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 viewpoint that it can be easily separated collectively with a slight force at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) Therefore, the pressure-sensitive adhesive layer (X1) is preferably 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 heat treatment for separation 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 to 300 μm.

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

In the present specification, for example, as shown in FIG. 2, in the case where the pressure-sensitive adhesive sheet (I) has a plurality of pressure-sensitive adhesive layers, the above “thickness of the pressure-sensitive adhesive layer (X1)” is the pressure-sensitive adhesive The thickness of the agent 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 separation heat treatment [(Y1-1) / (X1 ] Is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, and still more preferably 30 or less.
If the thickness ratio is 1000 or less, it is easily separated collectively by a slight force at the interface P between the adhesive sheet (I) and the base material (Y2) of the resin film forming sheet (II) by heat treatment. An adhesive laminate can be made possible.
The thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1.0 or more, and still more preferably 5.0 or more.

In the pressure-sensitive adhesive sheet (I) of the first embodiment, the substrate (Y1) is composed of only the heat-expandable substrate layer (Y1-1) as shown in FIG. 1 (a), As shown in FIG. 1 (b), it also has a thermally expandable base material layer (Y1-1) on the resin film forming sheet (II) side, and is not thermally expandable on the pressure-sensitive adhesive layer (X1) side. It may have a base material layer (Y1-2).

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 separation 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 | grains on both surfaces of a base material (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 heat-expandable pressure-sensitive adhesive layer, and the substrate (Y2) of the resin film-forming sheet (II) are in direct contact .
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 which is a non-heat-expandable pressure-sensitive adhesive layer The thickness ratio to (X12) [(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 base material (Y1) before heat treatment for separation As X11) / (Y1)], it 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 that expand by heating, but are preferably particles whose expansion start temperature (t) is adjusted to 60 to 270.degree. The expansion start temperature (t) is appropriately selected according to the application 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.

(Measurement method of 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. And. Heating is performed from 20 ° C to 300 ° C at a temperature increase rate of 10 ° C / min while a force of 0.01 N is applied by a pressure element, and the amount of displacement of the pressure element in the vertical direction is measured. Let the temperature be the 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 diameter of the thermally expandable particles before expansion is the volume median particle diameter (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)>
In the adhesive laminate of one embodiment of the present invention, when the substrate (Y1) of the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing thermally expandable particles, the thermally expandable group The material layer (Y1-1) preferably satisfies 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 or less is there.
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 expansion of the thermally expandable particles, the storage elastic modulus E ′ of the thermally expandable base material layer (Y1-1) decreases with the temperature rise. 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, in order to be easily separable by a slight force at the interface P between the adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation, the expansion start temperature (t) or more It is necessary to make it easy to form an unevenness | corrugation in the surface on the side laminated | stacked with the base material (Y2) of adhesive sheet (I) by heating to the temperature of (1).
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 resin film forming sheet (II) Irregularities are easily formed on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with the substrate (Y2).
As a result, it is possible to form an adhesive laminate which can be easily separated with a slight force at the interface P between the adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation.

The storage elastic modulus E ′ (t) defined in the requirement (1) of the thermally expandable base material layer (Y1-1) used in the present invention is preferably 9.0 × 10 ⁶ Pa or less, more preferably from the above viewpoint Is 8.0 × 10 ⁶ Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, still more preferably 4.0 × 10 ⁶ Pa or less.
In addition, the flow of the expanded thermally expandable particles is suppressed, and the shape maintenance of the unevenness formed on the surface of the pressure-sensitive adhesive sheet (I) on the side laminated with the substrate (Y2) of the resin film forming sheet (II) The storage elastic modulus E ′ (t) defined in the requirement (1) of the thermally expandable base material layer (Y1-1) is from the viewpoint of improving the properties and making it easier to separate with a slight force at the interface P 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.

From the viewpoint of setting the thermally expandable substrate layer (Y1-1) satisfying the above requirement (1), the content of the thermally expandable particles in the thermally expandable substrate layer (Y1-1) is the thermally expandable substrate Preferably 1 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, still more preferably 15 to 50% by mass with respect to the total mass (100% by mass) of the layer (Y1-1) It is 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, more preferably 0.001 to 20 parts by mass with respect to 100 parts by mass of the resin. It is 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 above requirement (1), the resin contained in the resin composition (y) is selected from acrylic urethane resins and olefin resins. It is preferable to include one or more of the following.
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.

(Acrylic 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 Cellulose: triacetate cellulose; polycarbonate; polyurethane not corresponding to acrylic urethane resin; polysulfone; polyetheretherketone; polyethersulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; A fluorine resin etc. are mentioned.

However, from the viewpoint of forming the thermally expandable base material layer (Y1-1) satisfying the above requirement (1), the content ratio of the resin other than the acrylic urethane resin and the olefin resin in the resin composition (y) is The smaller one is preferable.
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 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.
It is easy to form the thermally expandable base material layer (Y1-1) satisfying the above requirement (1) by irradiating the coating film formed from the solvent-free resin composition (y1) with an energy ray.

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.
In addition, 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, and a polymerization initiator.
Hereinafter, each component contained in an adhesive composition (x1) is demonstrated.
Even when the pressure-sensitive adhesive sheet (I) has the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12), the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12) are also It can form from the adhesive composition (x1) containing each component shown below.

(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.

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 a 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, it is preferable that the adhesive resin contains an acrylic resin from the viewpoint of developing excellent adhesive strength.
When using the pressure-sensitive adhesive sheet (I) having the first pressure-sensitive adhesive layer (X11) and the second pressure-sensitive adhesive layer (X12), the first pressure-sensitive adhesive layer (X11) in contact with the resin film-forming sheet (II) By containing an acrylic resin, it is possible to easily form asperities on the surface of the first pressure-sensitive adhesive layer.

The content ratio of the acrylic resin in the adhesive resin is preferably 30 to 100 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 (p1) derived from an alkyl (meth) acrylate (p1 ′) (hereinafter also referred to as “monomer (p1 ′)”) and a functional group-containing monomer (p2) The acrylic copolymer (P) having a structural unit (p2) derived from ') (hereinafter also referred to as "monomer (p2')") is more preferable.

The number of carbon atoms of the alkyl group of the monomer (p1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, still more preferably 4 to 8 from the viewpoint of improving adhesion properties. It is.
In addition, the alkyl group which a monomer (p1 ') has may be a linear alkyl group, and a branched alkyl group may be sufficient.

As the monomer (p1 ′), 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 (p1 ') may be used alone or in combination of two or more.
As the monomer (p1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.

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

As a functional group which monomer (p2 ') has, a hydroxyl group, a carboxy group, an amino group, an epoxy group etc. are mentioned, for example.
That is, as a monomer (p2 '), 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 (p2 ') may be used alone or in combination of two or more.
Among these, as the monomer (p2 '), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.

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

The acrylic copolymer (P) may further have a structural unit (p3) derived from another monomer (p3 ′) other than the monomers (p1 ′) and (p2 ′).
In the acrylic copolymer (P), the content of the structural units (p1) and (p2) is preferably 70 based on the total structural units (100% by mass) of the acrylic copolymer (P). 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 (p3 ') 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.

In addition, the acrylic copolymer (P) may be an energy ray-curable acrylic copolymer in which a polymerizable functional group is introduced to 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 (p1) and (p2) and the functional group possessed by the structural unit (p2) 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 cross-linking agent, as in the case of the above-mentioned acrylic copolymer (P), when containing a pressure-sensitive resin having a functional group. 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.

(Photopolymerization initiator)
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.
By containing a photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with energy rays of relatively low energy.
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.

(Additive 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 the adhesive sheet (I) of the above-mentioned 2nd aspect which the adhesive laminated body 2 shown in FIG. 3 has, the 1st adhesive layer (X11) which is a heat-expandable adhesive layer is further It is formed from a thermally expandable pressure sensitive adhesive composition (x11) containing thermally expandable particles.
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 content of the heat-expandable particles in the non-heat-expandable pressure-sensitive adhesive composition which is a forming material of the non-heat-expandable pressure-sensitive adhesive layer is It is preferable that the amount be as small as possible.
The content of the thermally expandable particles is preferably based on the total amount (100% by mass) of the active ingredients of the non-thermally expandable adhesive composition or the total mass (100% by mass) of the non-thermally expandable adhesive layer. It is less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass.

A pressure-sensitive adhesive sheet (I) having a first pressure-sensitive adhesive layer (X11) and a second pressure-sensitive adhesive layer (X12), which is a non-heat-expandable pressure-sensitive adhesive layer, as pressure-sensitive adhesive laminates 1c and 1d shown in FIG. Storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11) which is a non-heat-expandable pressure-sensitive adhesive layer at 23 ° C. is preferably 1.0 × 10 ⁸ Pa or less, preferably Preferably it is 5.0 * 10 < ⁷ > Pa or less, More preferably, it is 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. When it is configured as 1c, 1d, it is in contact with the resin film forming sheet (II) by the expansion of the thermally expandable particles in the thermally expandable base material layer (Y1-1) by the separation heat treatment. Irregularities are easily formed on the surface of the first pressure-sensitive adhesive layer (X11). As a result, it is possible to provide an adhesive laminate which can be easily separated at once with a slight force at the interface P between the adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation. .
The storage shear modulus G ′ (23) of the first pressure-sensitive adhesive layer (X11), which is a non-thermally expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5 .0 × ¹⁰ 4 Pa or more, further preferably 1.0 × ¹⁰ 5 Pa or more.

[Composition of sheet (II) for resin film formation]
In the adhesive laminate of the present invention, the resin film-forming sheet (II) has a curable resin layer (Z2) on one surface side of the substrate (Y2), and the other surface of the substrate (Y2) Adhesive sheet (I) is directly laminated on the side.
Moreover, in the adhesive laminate of one embodiment of the present invention, the resin film-forming sheet (II) has an adhesive layer (X2) between the base material (Y2) and the curable resin layer (Z2). It may be done.

Here, the base material (Y2) is a base material (Y2) from the viewpoint of being able to be easily separated collectively with a slight force at the interface P between the base material (Y2) of the sheet (II) for resin film formation and the adhesive sheet (I). And a non-thermally expandable substrate.
The volume change rate (%) of the substrate (Y2) calculated from the above formula is less than 5%, but preferably less than 2%, more preferably less than 1%, still more preferably less than 0.1% Even more preferably, it is less than 0.01%.
Hereinafter, a base material (Y2), a curable resin layer (Z2), and an adhesive layer (X2) are demonstrated.

<Base material (Y2)>
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).
In addition, it is preferable that a base material (Y2) contains resin, and it is more preferable that the resin layer containing resin is formed in the surface of the base material (Y2) of the side laminated with an adhesive sheet (I) at least. More preferably, the substrate (Y2) is a resin film or a resin sheet.
In addition, the surface on the side of the adhesive sheet (I) of the base material (Y2) on which the pressure-sensitive adhesive sheet (I) is laminated is subjected to peeling treatment from the viewpoint of enabling separation simultaneously and easily with a slight force at interface P after heat treatment for separation. Is preferred.

In addition, from the viewpoint of making it easy to prevent positional deviation when attaching a processing object such as a semiconductor chip to the curable resin layer (Z2), and when attaching the processing object, curing resin at heating The storage elastic modulus E ′ (23) at 23 ° C. of the substrate (Y2) is 1.0 × 10 ⁶ Pa or more from the viewpoint of making it easy to prevent excessive sinking into the layer (Z2) Is preferred.

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.

<Curable resin layer (Z2)>
The curable resin layer (Z2) may be formed of a composition which can be cured to form a cured resin film, but a curable composition (a polymer component (A) and a curable component (B) Preferably it is a layer formed from z).
The curable composition (z) may further contain one or more selected from a colorant (C), a coupling agent (D), and an inorganic filler (E).
In addition, the curable composition (z) further contains a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a gettering agent, and a chain transfer, as long as the effects of the present invention are not impaired. You may contain additives, such as an agent.
The components (A) to (F) contained in the curable composition (z) which is a forming material of the curable resin layer (Z2) will be described below.

(Polymer component (A))
The polymer component (A) contained in the curable composition (z) means a compound having a mass average molecular weight of 20,000 or more and having at least one repeating unit. By containing the polymer component (A) in the curable resin layer (Z2), flexibility and film forming property are mainly imparted to the curable resin layer (Z2), and sheet property maintaining property is good. can do.
The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, more preferably 50,000 to 2,000,000, further preferably 100,000 to 1,500,000 More preferably, it is 200,000 to 1,000,000.

The content of the component (A) is preferably 5 to 100 parts by mass with respect to the total amount (100% by mass) of the active ingredients of the curable composition (z) or the total mass (100% by mass) of the curable resin layer (Z2). It is 50% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 30% by mass.
The polymer component (A) may be used alone or in combination of two or more.
Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber polymers and the like.
In addition, in this specification, although the acrylic polymer (A1) which has an epoxy group, and the phenoxy resin which has an epoxy group have thermosetting property, it corresponds to the above-mentioned "polymer component." If present, they are not included in the curable component (B) but in the concept of the polymer component (A).

Among these, it is preferable that a polymer component (A) contains an acryl-type polymer (A1).
The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100% by mass, more preferably 70 to 100% by mass based on the total amount (100% by mass) of the polymer component (A) The content is 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.

(Acrylic polymer (A1))
The mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3,000,000, more preferably 100,000, from the viewpoint of imparting flexibility and film forming property to the curable resin layer (Z2). It is preferably 1.5 to 1,000,000, more preferably 150,000 to 1,200,000 and still more preferably 250,000 to 1,000,000.

The glass transition temperature (Tg) of the acrylic polymer (A1) is the adhesion of the curable resin layer (Z2) to the adherend, and the resin produced using the resin film-forming sheet (II) From the viewpoint of improving the reliability of the film-processed object, it is preferably at -60 to 50 ° C, more preferably -50 to 30 ° C, still more preferably -40 to 10 ° C, still more preferably -35 to 5 ° C is there.

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

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

From the viewpoint of improving the reliability of the resin film-formed object to be processed produced using the resin film-forming sheet (II), the monomer (a1 ′) is an alkyl (meth) having an alkyl group of 1 to 3 carbon atoms. It is preferable to include an acrylate, and more preferable to include a methyl (meth) acrylate.
From the above viewpoint, the content of the structural unit (a11) derived from the alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is relative to the total structural units (100% by mass) of the acrylic polymer (A1) Preferably, it is 1 to 80% by mass, more preferably 5 to 80% by mass, and still more preferably 10 to 80% by mass.

From the viewpoint of raising the gloss value of the resin film of the object to be processed with a resin film produced using the resin film-forming sheet (II) to improve the laser marking suitability, the monomer (a1 ′) is carbon It is preferable to include an alkyl (meth) acrylate having an alkyl group of 4 or more, and more preferably include an alkyl (meth) acrylate having an alkyl group having 4 to 6 carbon atoms, and include butyl (meth) acrylate More preferable.
From the above viewpoint, the content of the structural unit (a12) derived from the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms (preferably 4 to 6, more preferably 4) is an acrylic polymer (A1) The amount is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and still more preferably 10 to 60% by mass, based on 100% by mass of all structural units of (1).

The content of the structural unit (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, still more preferably 55% by mass, relative to the total constituent units (100% by mass) of the acrylic polymer (A1). It is at most 90% by mass, more preferably 60 to 90% by mass.

Although the same thing as the above-mentioned monomer (p2 ') is mentioned as a monomer (a2'), 1 or more types chosen from a hydroxyl-group containing monomer and an epoxy-group containing monomer are preferable.
The monomers (a2 ′) may be used alone or in combination of two or more.

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

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

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

In addition, in the range which does not impair the effect of this invention, an acryl-type polymer (A1) may have a structural unit derived from monomers other than said structural unit (a1) and (a2).
Other monomers include, for example, vinyl acetate, styrene, ethylene, α-olefin and the like.

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

As a thermosetting component (B1), it is preferable to contain the compound which has a functional group which reacts at least by heating.
The energy ray-curable component (B2) contains a compound (B21) having a functional group that reacts by energy ray irradiation, and polymerizes and hardens when it is irradiated with energy rays such as ultraviolet rays and electron beams.
The functional groups possessed by these curable components react with one another to form a three-dimensional network structure, whereby curing is realized.

In addition, when using a thermosetting component (B1), when making it harden | cure before hardening resin layer (Z2) formed is isolate | separated by the interface P, it heats at temperature less than thermal expansion start temperature (t) And cure.
When the energy ray curable component (B2) is used, the curable resin layer (Z2) to be formed is irradiated with energy and cured separately from the heat treatment.

The mass average molecular weight (Mw) of the curable component (B) suppresses the viscosity of the composition for forming the curable resin layer (Z2) by using it in combination with the component (A), and improves the handleability. From the viewpoint of reducing the viscosity, it is preferably less than 20,000, more preferably 10,000 or less, and still more preferably 100 to 10,000.

(Thermosetting component (B1))
As a thermosetting component (B1), an epoxy-type thermosetting component is preferable.
It is preferable to use what combined the thermosetting agent (B12) with the epoxy compound (B11) which is a compound which has an epoxy group as an epoxy-type thermosetting component.

As an epoxy compound (B11), For example, a polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated substance, ortho cresol novolac epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin The epoxy compound etc. which have bifunctional or more in molecule | numerators, such as a bisphenol F-type epoxy resin and a phenylene frame-type epoxy resin, and whose mass mean molecular weight is less than 20,000 are mentioned.
You may use these epoxy compounds (B11) individually or in combination of 2 or more types.

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

(Thermosetting agent (B12))
The heat curing agent (B12) functions as a curing agent for the epoxy compound (B11).
As a thermosetting agent, the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule is preferable.
Examples of the functional group include phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group, and acid anhydride. Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable, a phenolic hydroxyl group or an amino group is more preferable, and an amino group is still more preferable.

As a phenol type thermosetting agent which has a phenol group, polyfunctional phenol resin, biphenol, novolak type phenol resin, dicyclopentadiene type phenol resin, zyloc type phenol resin, aralkyl phenol resin etc. are mentioned, for example.
As an amine thermosetting agent which has an amino group, dicyandiamide (DICY) etc. are mentioned, for example.
These thermosetting agents (B12) may be used alone or in combination of two or more.

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

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

As the curing accelerator (B13), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; tributylphosphine, diphenylphosphine, triphenylphosphine etc. Organic phosphines; and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate.
You may use these hardening accelerators (B13) individually or in combination of 2 or more types.

Content of a hardening accelerator (B13) is a viewpoint of the adhesive improvement of a curable resin layer (Z2), and the reliability of the processing object with a resin film manufactured using sheet | seat (II) for resin film formation From the viewpoint of improvement of the amount, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, further preferably 100 parts by mass of the total amount of the epoxy compound (B11) and the thermosetting agent (B12). Preferably, it is 0.3 to 4 parts by mass.

(Energy ray curable component (B2))
As the energy ray-curable component (B2), a compound (B21) having a functional group that reacts by energy ray irradiation may be used alone, but in combination with the compound (B21), a photopolymerization initiator (B22) may be used. It is preferred to use.

(Compound (B21) having a functional group capable of reacting by energy ray irradiation)
Examples of the compound (B21) having a functional group capable of reacting by energy ray irradiation (hereinafter also referred to as “energy ray reactive compound (B21)”) include trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate , Dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, oligoester acrylate, urethane acrylate based oligomer, epoxy acrylate, polyether acrylate, itaconcon An acid oligomer etc. are mentioned.
These energy ray reactive compounds (B21) may be used alone or in combination of two or more.
The mass average molecular weight (Mw) of the energy ray reactive compound (B21) is preferably 100 to 30,000, more preferably 300 to 10,000.

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

(Photoinitiator (B22))
By using together with the above-mentioned energy ray reactive compound (B21) and the photopolymerization initiator (B22), the polymerization curing time is shortened, and curing of the curable resin layer (Z2) is carried out even if the light irradiation amount is small. It can be advanced.
As a photoinitiator (B22), 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 (B22) is preferably 0.1 with respect to 100 parts by mass of the energy ray reactive compound (B21) from the viewpoint of sufficiently advancing the curing reaction and suppressing the formation of the residue. The amount is about 10 parts by mass, more preferably 1 to 5 parts by mass.

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

<Colorant (C)>
The curable resin layer (Z2) preferably further contains a colorant (C).
By including the colorant (C) in the curable resin layer (Z2), an object to be processed having a resin film formed from the curable resin layer (Z2), for example, a semiconductor chip having a resin film, is incorporated in an apparatus In this case, infrared rays and the like generated from surrounding devices can be shielded to prevent malfunction of the semiconductor chip.

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

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

<Coupling agent (D)>
The curable resin layer (Z2) preferably further contains a coupling agent (D).
By including the coupling agent (D), the polymer component in the curable resin layer (Z2) is combined with the surface of the object to be processed such as a semiconductor chip and the surface of the filler to improve adhesion and cohesion. be able to. Moreover, water resistance can also be improved, without impairing the heat resistance of the resin film formed from a curable resin layer (Z2).

As a coupling agent (D), the compound which reacts with the functional group which a component (A) or a component (B) has is preferable, and a silane coupling agent is more preferable.
As a silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (methacryloxy) Propyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfane, methyltri Methoxysilane And methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane and the like.
These (D) coupling agents may be used alone or in combination of two or more.

As a coupling agent (D), an oligomer type coupling agent is preferable.
The molecular weight of the coupling agent (D) including an oligomer type coupling agent is preferably 100 to 15,000, more preferably 150 to 10,000, more preferably 200 to 5,000, still more preferably 250 to 3,000, and still more preferably Is 350-2000.

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

<Inorganic filler (E)>
The curable resin layer (Z2) preferably further contains an inorganic filler (E).
By including the inorganic filler (E), it is possible to adjust the thermal expansion coefficient in the resin film after curing of the curable resin layer (Z2) to an appropriate range, and it is possible to process an object such as a semiconductor chip The thermal expansion coefficient of the resin film after curing can be optimized, and a product including the resin film formed by the curable resin layer (Z2) and the processing object, for example, when the processing object is a semiconductor chip Can improve the reliability of the semiconductor chip. Moreover, it also becomes possible to reduce the moisture absorption rate of the resin film after hardening.

The inorganic filler (E) may be any non-thermal expandable material, for example, powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, etc. And thermally expandable particles such as single crystal fibers and glass fibers.
These inorganic fillers (E) may be used alone or in combination of two or more.
Among these, silica or alumina is preferable.

The average particle diameter of the inorganic filler (E) is preferably from the viewpoint of improving the gloss value of the resin film of the object to be processed with a resin film produced using the resin film-forming sheet (II). The thickness is preferably 3 to 50 μm, more preferably 0.5 to 30 μm, and still more preferably 0.7 to 10 μm.

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

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

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

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

<Peeling material>
In the pressure-sensitive adhesive laminate of one embodiment of the present invention, a release material may be further laminated on the surface of the pressure-sensitive adhesive layer (X1) and the curable resin layer (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.

[Manufacturing method of object to be processed with resin film]
The adhesive laminate of the present invention can fix the object to be processed to a support and carry out predetermined processing, and can be easily separated from the support collectively with a slight force after processing. And, after separation, it is possible to obtain a processing object with a resin film capable of forming a cured resin film.
Therefore, by using the adhesive laminate of the present invention, an operation of sticking an adhesive sheet to a processing object to fix the processing object to a support before processing, and removing the adhesive sheet from the processing object after processing Then, the operation of attaching the resin film forming sheet can be performed at one time, and improvement in productivity can be expected.

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

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

<Step (α-1)>
In the step (α-1), the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) It is the process of mounting or sticking a processing target on the surface of Z2).
Fig.4 (a) is a cross-sectional schematic diagram which shows the state which fixed the process target object to the support body through the adhesive laminated body 1a of the 1st aspect of this invention shown to FIG. 1 (a).
In the step (α-1), as shown in FIG. 4A, the object to be processed 60 is fixed to the support 50 through the adhesive laminate 1a of the first aspect of the present invention, The adhesive laminate and the processing inspection object are laminated in this order.
In addition, in FIG. 4, although the example using the adhesive laminated body 1a shown to Fig.1 (a) is shown, also when using the adhesive laminated body of this invention which has another structure, it carries out similarly. The support, the adhesive laminate, and the processing inspection object are laminated in this order.

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

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

The material constituting the support is appropriately selected in consideration of the required characteristics such as mechanical strength and heat resistance according to the type of the processing object and the processing applied in the step (α-2). Be done.
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 the type of processing in the next step and the like, but is preferably 20 μm to 50 mm, and more preferably 60 μm to 20 mm.

The temperature condition in the step (α-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). When it is ° C., it is preferable to carry out in an environment below the expansion start temperature (t)).

<Step (α-2)>
The step (α-2) is a step of carrying out predetermined processing on the object to be processed which is attached to the curable resin layer (Z2) of the adhesive laminate of the present invention in the step (α-1).
Examples of processing to be performed in the step (α-2) include sealing processing on a target object using a resin, grinding processing of the target object, dicing (individualization) processing, circuit formation processing, etching processing, plating processing, sputtering A process, a vapor deposition process, a lamination process using the adhesive sheet prepared separately, etc. are mentioned.
In this step (α-2), two or more of these processes may be performed in combination.

As a temperature condition in the step (α-2), it is preferable to be carried out under a temperature environment lower than the expansion start temperature (t) of the thermally expandable particles.
In addition, in the step (α-2), the curable resin layer (Z2) may be cured to form a cured resin film in parallel with the above processing. For example, in the case where the processing performed in this step is processing involving heating, the heat can cure the curable resin layer (Z2) to form a cured resin film.

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

<Step (α-3)>
In the step (α-3), the interface between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation by heating at the thermal expansion start temperature (t) or more of the thermally expandable particles. It is a process of separating by P and obtaining a processing object with a resin film.
FIG. 4B is a schematic cross-sectional view showing a state of being separated at the interface P by the heat treatment.
FIG. 4B shows a state in which the object to be processed and inspected is separated in the state of being laminated on the resin film forming sheet (II) by the heat treatment.

The “temperature above expansion start temperature (t)” in the heat treatment in the step (α-3) is “expansion start temperature (t) + 10 ° C.” or more and “expansion start temperature (t) + 60 ° C.” or less The temperature is preferably “expansion start temperature (t) + 15 ° C.” or more and “expansion start temperature (t) + 40 ° C.” or less.

Here, the heat source at the time of heat treatment is preferably provided on the support side. It can be easily separated at the interface P between the adhesive sheet (I) of the adhesive laminate and the base (Y2) of the sheet (II) for resin film formation.

In this manner, after separation at the interface P, it is possible to obtain a processing object with a resin film in which the resin film forming sheet (II) is attached to the processing object.
Even after separation, when the curable resin layer (Z2) is not cured, a cured resin film can be formed by curing the curable resin layer (Z2).
After forming the cured resin film, the resin film forming sheet (II) other than the curable resin layer (Z2) can be removed to obtain a processing object with a cured resin film.

[Method of producing a cured sealing film with a cured resin film]
By using the pressure-sensitive adhesive laminate of the present invention, productivity can be improved, and a cured resin film-attached cured sealing material can also be produced.
As a more specific method for producing a cured sealing film with a cured resin film, a production method having the following steps (β-1) to (β-3) can be mentioned.
Step (β-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) Step / Step (β-2) of placing a semiconductor chip on Z2): the semiconductor chip is covered with a sealing material, and the sealing material is cured to cure and seal the semiconductor chip And curing the curable resin layer (Z2) to form a cured resin film / step (β-3): adhesion at the heat expansion start temperature (t) or more of the thermally expandable particles A step of separating at the interface P between the sheet (I) and the base material (Y2) of the sheet (II) for resin film formation to obtain a cured resin film-attached cured sealing body

<Step (β-1)>
In the step (β-1), the surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) This is a step of mounting the semiconductor chip on Z2).
The above-mentioned support used in the step (β-1) 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.
The semiconductor chip is preferably mounted so that the back surface opposite to the circuit surface is covered with the surface of the curable resin layer (Z2) of the sheet (II) for forming a resin film. In this case, after mounting, the circuit surface of the semiconductor chip is exposed.
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, the semiconductor chip is covered with a sealing material in a region larger than the chip size, such as FOWLP and FOPLP, and the rewiring layer is formed not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material. Preferably applied to the package.
Therefore, the semiconductor chip is mounted on a part of the surface of the curable resin layer (Z2), and the plurality of semiconductor chips are mounted on the surface in a state where they are aligned at a constant interval. It is preferable that the plurality of semiconductor chips CP be mounted on the surface in a state of being aligned in a matrix form of a plurality of rows and a plurality of columns at regular intervals.
The distance between the semiconductor chips may be appropriately determined in accordance with the form of the target package and the like.

<Step (β-2)>
In the step (β-2), the semiconductor chip is covered with a sealing material (hereinafter, also referred to as “covering treatment”), the sealing material is cured (hereinafter, also referred to as “hardening treatment”), In this step, a cured sealing body in which a chip is sealed and a curable resin layer (Z2) are cured to form a cured resin film.
In the covering process of the step (β-2), first, the semiconductor chip and at least the peripheral portion of the semiconductor chip on the surface of the curable resin layer (Z2) are 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 the coating treatment is performed, the sealing material is cured to obtain a cured sealing body in which the semiconductor chip is sealed with the cured sealing material.
The coating treatment and curing treatment in the step (β-2) are preferably performed under temperature conditions lower than the expansion start temperature (t) of the thermally expandable particles.
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.

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

<Step (β-3)>
In the step (β-3), the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the resin film-forming sheet (II) are heated by heating the thermal expansion particles at a thermal expansion start temperature (t) or more. It is a step of separating at the interface P to obtain a cured sealing film with a cured resin film.
By heating at the thermal expansion start temperature (t) or more, the thermally expandable particles expand, and unevenness is generated on the surface of the pressure-sensitive adhesive sheet (I) on the substrate (Y2) side of the resin film forming 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 (β-3) are as described above.

After separation at the interface P, by removing the layer for the resin film formation sheet (II) other than the curable resin layer (Z2), a cured resin film-attached cured sealing body can be obtained.
Thereafter, the cured sealing body is ground until the circuit surface of the semiconductor chip is exposed, rewiring is performed on the circuit surface, an external electrode pad is formed, and the external electrode pad and the external terminal electrode are connected. And so on. In addition, after the external terminal electrode is connected to the cured and sealed body, the semiconductor device can be manufactured by separating it into pieces.

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 (X11) and (X12)>
The formed pressure-sensitive adhesive layers (X11) and (X12) 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 for separation>
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.

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

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 mass 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.

Production Example 3 (Preparation of Curable Composition)
Each component of the kind and compounding amount (all “active ingredient ratio”) shown below is compounded, it is further diluted with methyl ethyl ketone, and it stirs uniformly and hardens composition of solid content concentration (active ingredient concentration) 61 mass% Solution was prepared.
Acrylic polymer: Compounding amount = 28 parts by mass n-butyl acrylate 10 parts by mass, methyl acrylate 70 parts by mass, glycidyl methacrylate 5 parts by mass, and 2-hydroxyethyl acrylate 15 parts by mass Combined (mass average molecular weight: 800,000, glass transition temperature: -1 ° C.), corresponding to the component (A1).
-Epoxy compound (1): compounding amount = 10.4 parts by mass Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER 828", epoxy equivalent = 184 to 194 g / eq), equivalent to the above component (B11) .
-Epoxy compound (2): compounding amount = 5.2 parts by mass Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, product name "Epiclon HP-7200HH", epoxy equivalent = 255 to 260 g / eq), the above component (B11) Equivalent to).
-Epoxy compound (3): compounding amount = 1.7 parts by mass Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent = 800 to 900 g / eq), equivalent to the above component (B11) .
Thermosetting agent: Compounding amount = 0.42 parts by mass Dicyandiamide (manufactured by ADEKA, product name “Adeca Hardener EH-3636AS”, active hydrogen content = 21 g / eq), corresponds to the component (B12).
Curing accelerator: compounding amount = 0.42 parts by mass 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name "Cuazole 2PHZ"), corresponding to the component (B13).
-Coloring agent: Compounding amount = 0.20 parts by mass Carbon black (manufactured by Mitsubishi Chemical Corporation, product name "# MA650", average particle diameter = 28 nm), corresponds to the component (C).
Silane coupling agent: compounding amount = 0.09 parts by mass 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM 403"), corresponding to the component (D).
Inorganic filler: compounding amount = 55.5 parts by mass Silica filler (manufactured by Admatechs, product name “SC2050MA”, average particle diameter = 0.5 μm), which corresponds to the component (E).

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

<Adhesive resin>
Acrylic copolymer (i): 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).

<Additives>
-Isocyanate crosslinking agent (i): Tosoh Co., Ltd. make, product name "Coronato L", solid content concentration: 75 mass%.
Photopolymerization initiator (i): manufactured by BASF, product name “IRGACURE 184”, 1-hydroxy-cyclohexyl-phenyl-ketone.

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

[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 exposed is a sheet for forming a resin film (II) The surface to which the peeling process of the heavy release film which is a base material (Y2) was not performed was bonded, and the adhesive laminated body was obtained.

About the said adhesive laminated body, the interface P of 1st adhesive layer (X11) of adhesive sheet (I), and base material (Y2) of resin film formation sheet (II) before heat processing and after heat processing Peeling force (F ₁ ) and (F ₂ ) at the time of separation by were measured according to 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
A cured resin film-attached cured sealing body was produced by the following procedure.
(1) Mounting of semiconductor chip The light release film on the adhesive sheet (I) side of the adhesive laminate prepared in Example 1 was removed, and the second adhesive layer (X12) of the adhesive sheet (I) was exposed. The adhesive surface of (a) was attached to a support (glass).
Then, the light peeling film on the resin film forming sheet (II) side is also removed, and nine semiconductor chips (each on the surface of the curable resin layer (Z2) of the resin film forming sheet (II) exposed are The chip size is 6.4 mm × 6.4 mm, and the chip thickness is 200 μm (# 2000), with the necessary spacing so that the back surface opposite to the circuit surface of each semiconductor chip contacts the surface. Placed.

(2) Formation of Cured Sealed Body The nine semiconductor chips and the surface of the curable resin layer (Z2) at least at the periphery of the semiconductor chip are covered with a sealing resin film, and a vacuum heating and pressing laminator is provided. 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 With the curing of the sealing resin film, the sheet (II) for forming a resin film The curable resin layer (Z2) was also cured in the above environment to form a cured resin film.

(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 adhesive layer (X11) of adhesive sheet (I), and the base material (Y2) of sheet | seat (II) for resin film formation.
Then, after separation, the base material (Y2) of the resin film-forming sheet (II) was also removed to obtain a cured resin film-attached cured sealing body.

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) Sheet for resin film formation (Y2) Substrate (Z2) Curable resin layer 50 Support 60 Object to be processed P Interface

Claims (13)

1. A thermally expandable pressure-sensitive adhesive sheet (I) which has a substrate (Y1) and a pressure-sensitive adhesive layer (X1) and which includes thermally expandable particles in any layer;
   And a sheet (II) for forming a resin film having a substrate (Y2) and a curable resin layer (Z2),
   The pressure-sensitive adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation are directly laminated,
   An adhesive laminate used to fix an object to be processed to a support when predetermined processing is performed,
   The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support,
   The surface of the curable resin layer (Z2) of the sheet (II) for resin film formation is a surface to which the object to be processed is attached,
   Separating at the interface P between the pressure-sensitive adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation by heat treatment at a temperature higher than the thermal expansion start temperature (t) of the thermally expandable particles Is an adhesive laminate.
2. The pressure-sensitive adhesive laminate according to claim 1, wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270 ° C.
3. The pressure-sensitive adhesive laminate according to claim 1 or 2, wherein the substrate (Y1) of the pressure-sensitive adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing the thermally expandable particles.
4. The adhesive property according to claim 3, wherein the substrate (Y1) of the pressure-sensitive adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). Stack.
5. The thermally expandable substrate layer (Y1-1) of the substrate (Y1) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the sheet (II) for resin film formation are directly laminated. The adhesive laminated body as described in 3 or 4.
6. The adhesive sheet (I) has a configuration in which the base material (Y1) is held between the first adhesive layer (X11) and the second adhesive layer (X12),
   The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the sheet (II) for forming a resin film are directly laminated,
   The pressure-sensitive adhesive laminate according to any one of claims 3 to 5, wherein a surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support.
7. The adhesive sheet (I) has a configuration in which the base material (Y1) is held between the first adhesive layer (X11) and the second adhesive layer (X12),
   The first pressure-sensitive adhesive layer (X11) is a heat-expandable pressure-sensitive adhesive layer containing the heat-expandable particles,
   The second pressure-sensitive adhesive layer (X12) is a non-heat-expandable pressure-sensitive adhesive layer,
   The first pressure-sensitive adhesive layer (X11) of the pressure-sensitive adhesive sheet (I) and the substrate (Y2) of the sheet (II) for forming a resin film are directly laminated,
   The pressure-sensitive adhesive laminate according to claim 1 or 2, wherein the surface of the second pressure-sensitive adhesive layer (X12) of the pressure-sensitive adhesive sheet (I) is a surface to be attached to the support.
8. The pressure-sensitive adhesive laminate according to any one of claims 1 to 7, wherein the surface of the substrate (Y2) on which the pressure-sensitive adhesive sheet (I) is laminated is a surface subjected to release treatment.
9. The curable resin layer (Z2) is a layer formed from a curable composition (z) containing a polymer component (A) and a curable component (B), according to any one of claims 1 to 8, Adhesive laminate as described.
10. A method for producing an object to be processed with a resin film, using the adhesive laminate according to any one of claims 1 to 9,
    A method for producing a processing object having a resin film, comprising the following steps (α-1) to (α-3):
    Step (α-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) Step / Step (α-2) of placing or sticking the object to be processed on the surface of Z2): Step / step (α-3) of performing predetermined processing on the object: heat of the thermally expandable particles A process of obtaining an object to be processed with a resin film by separating at the interface P between the adhesive sheet (I) and the base material (Y2) of the sheet (II) for resin film formation by heating at expansion start temperature (t) or higher
11. The method for producing a processing object with a resin film according to claim 10, wherein in the step (α-2), the curable resin layer (Z2) is cured to form a cured resin film.
12. The method for producing a processing target object with a resin film according to claim 10, comprising the following step (α-2 ') after the step (α-2) and before the step (α-3).
    Step (α-2 ′): a step of curing the curable resin layer (Z2) to form a cured resin film.
13. A method for producing a cured sealing film with a cured resin film, using the adhesive laminate according to any one of claims 1 to 9,
    A method for producing a cured molded article with a cured resin film, comprising the following steps (β-1) to (β-3):
    Step (β-1): The surface of the pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate is attached to a support and a curable resin layer of the resin film-forming sheet (II) Step / Step (β-2) of placing a semiconductor chip on Z2): the semiconductor chip is covered with a sealing material, and the sealing material is cured to cure and seal the semiconductor chip And curing the curable resin layer (Z2) to form a cured resin film / step (β-3): adhesion at the heat expansion start temperature (t) or more of the thermally expandable particles A step of separating at the interface P between the sheet (I) and the base material (Y2) of the sheet (II) for resin film formation to obtain a cured resin film-attached cured sealing body

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