KR102725244B1 - Adhesive laminate, method of using adhesive laminate, and method of producing cured encapsulation having cured resin film - Google Patents

Abstract

The present invention relates to an adhesive laminate comprising an expandable adhesive sheet (I) having a substrate (Y) and an adhesive layer (X), one of which contains expandable particles, and a cured resin film forming sheet (II) having a thermosetting resin layer (Z), wherein the adhesive sheet (I) and the thermosetting resin layer (Z) of the cured resin film forming sheet (II) are directly laminated, and wherein the laminate is formed by separating the adhesive sheet (I) and the cured resin film forming sheet (II) at an interface P by expanding the expandable particles.

Description

Adhesive laminate, method of using adhesive laminate, and method of producing cured encapsulation having cured resin film

The present invention relates to an adhesive laminate, a method for using the adhesive laminate, and a method for producing a cured encapsulation body having a cured resin film using the adhesive laminate.

Adhesive sheets are used not only for the purpose of permanently fixing a material, but also for the purpose of temporarily fixing the material to be processed or inspected, such as building materials, interior materials, and electronic components.

For these types of adhesive sheets for temporary fixing purposes, both adhesiveness during use and peelability after use are required.

For example, Patent Document 1 discloses a heat-peelable adhesive sheet for temporary fixation when cutting electronic components, wherein a heat-expandable adhesive layer containing heat-expandable microspheres is provided on at least one side of the substrate.

This heat-peelable adhesive sheet has a maximum particle size of heat-expandable microspheres adjusted with respect to the thickness of the heat-expandable adhesive layer, and the average roughness of the center line of the surface of the heat-expandable adhesive layer before heating is adjusted to 0.4 ㎛ or less.

Patent Document 1 describes that the heat-peelable adhesive sheet can exhibit adhesive properties that prevent adhesion defects such as chipping because it can secure a sufficient bonding area with the adherend when cutting an electronic component, and on the other hand, after use, by heating and expanding the heat-expandable microspheres, the contact area with the adherend is reduced, enabling easy peeling.

Patent Document 1: Japanese Patent No. 3594853

In a processing process using an adhesive sheet as described in Patent Document 1, an object to be processed (hereinafter also referred to as “object to be processed”) is temporarily fixed using an adhesive sheet, and after processing is performed on the object to be processed, the object to be processed is separated from the adhesive sheet.

However, there are cases where the above processing is performed by covering a processing target, such as a semiconductor chip, with a sealing material made of a curable resin and curing the sealing material to form a cured sealing body.

Here, when the above-described bagging process is performed using the adhesive sheet as described in Patent Document 1, and after forming a cured bag, when the adhesive sheet and the cured bag are separated by heating, the cured bag after separation tends to warp due to heat shrinkage.

A cured bag having an uneven surface due to warping is likely to cause problems such as cracks when the cured bag is ground in the next process, or defects are likely to occur when the cured bag is conveyed by an arm when the cured bag is returned by a device.

Additionally, there are cases where a resin film is further installed on one surface of a curing bag to create a curing bag having a resin film.

To manufacture a cured bag having such a resin film, it is usually necessary to go through a process of attaching a separately prepared resin film forming sheet to one surface of the formed cured bag, curing the resin film forming sheet, and forming a resin film.

In addition, since the cured bag body is prone to warping during manufacturing as described above, there are concerns about the deterioration of workability when attaching a sheet for forming a resin film due to warping of the cured bag body, as well as the deterioration of the adhesion between the cured resin film and the cured bag body.

In addition, the cured bag having the obtained resin film may also have a large warpage, which may cause various problems in the next process.

The present invention aims to provide an adhesive laminate capable of improving productivity by manufacturing a cured bag having a cured resin film, which can secure a bagging object to a support and perform bagging processing, and at the same time can be easily and collectively separated from the support with a weak force after bagging processing, and further has a flat surface by suppressing warping.

The present inventors have found that an adhesive laminate having an expandable adhesive sheet (I) having a substrate and an adhesive layer, one of which includes a layer containing expandable particles, and a sheet (II) for forming a cured resin film having a thermosetting resin layer (Z), can solve the above-mentioned problem.

That is, the present invention relates to the following [1] to [13].

[1] An expandable adhesive sheet (I) having a substrate (Y) and an adhesive layer (X), wherein one of the layers includes expandable particles, and

A sheet (II) for forming a cured resin film having a thermosetting resin layer (Z) is provided.

An adhesive laminate formed by directly laminating an adhesive sheet (I) and a thermosetting resin layer (Z) of a sheet (II) for forming a cured resin film,

An adhesive laminate, which is separated at the interface P between the adhesive sheet (I) and the sheet (II) for forming a cured resin film by a treatment for expanding the above-mentioned expandable particles.

[2] The adhesive laminate described in [1] above, wherein the expandable particles are heat-expandable particles.

[3] The adhesive laminate described in [1] or [2] above, wherein the thermosetting resin layer (Z) is a layer formed of a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B).

[4] The adhesive layer (X) of the adhesive sheet (I) is composed of a first adhesive layer (X1) and a second adhesive layer (X2).

The substrate (Y) is sandwiched between the first adhesive layer (X1) and the second adhesive layer (X2).

An adhesive laminate according to any one of [1] to [3] above, wherein the adhesive surface of the first adhesive layer (X1) has a configuration in which it is directly laminated with the thermosetting resin layer (Z).

[5] The substrate (Y) is an adhesive laminate according to any one of [1] to [4], having an expandable substrate layer (Y1) containing expandable particles.

[6] The adhesive laminate described in [5] above, wherein the adhesive layer (X) is a non-expandable adhesive layer.

[7] The substrate (Y) is an adhesive laminate as described in [5], having an intumescent substrate layer (Y1) and a non-intumescent substrate layer (Y2).

[8] A first adhesive layer (X1) is laminated on the surface of the expandable substrate layer (Y1),

An adhesive laminate as described in [7] above, having a configuration in which a second adhesive layer (X2) is laminated on the surface of a non-intumescent substrate layer (Y2).

[9] The adhesive laminate described in [8] above, wherein the first adhesive layer (X1) and the second adhesive layer (X2) are non-expandable adhesive layers.

[10] An adhesive laminate according to any one of [1] to [9], wherein the sheet (II) for forming a cured resin film is composed only of a thermosetting resin layer (Z).

[11] Place the bagging target on the surface of the sheet (II) for forming a cured resin film,

An adhesive laminate according to any one of the above [1] to [10], which is used to form a cured encapsulation body including the encapsulation object by covering the surface of the encapsulation object and at least the peripheral portion of the encapsulation object with an encapsulation material and thermally curing the encapsulation material.

[12] When the above-mentioned sealing material is heat-cured, the thermosetting resin layer (Z) can also be heat-cured to form a cured resin film.

An adhesive laminate as described in [11], which is used to obtain a cured encapsulated body having a cured resin film by separating the expandable particles at the interface P through an expansion treatment.

[13] A method of using an adhesive laminate as described in any one of the above [1] to [12],

Place the bagging object on the surface of the sheet (II) for forming a cured resin film,

A method for using an adhesive laminate, comprising covering the surface of the above-mentioned bagging object and at least the periphery of the above-mentioned bagging object and a sheet (II) for forming a cured resin film with a bagging material, and thermally curing the bagging material to form a cured bagging body including the above-mentioned bagging object.

[14] When the above-mentioned sealant is cured, the thermosetting resin layer (Z) is also cured to form a cured resin film.

A method for using the adhesive laminate described in [13], wherein the above expandable particles are separated from the interface P by an expanding treatment, thereby obtaining a cured encapsulated body having a cured resin film.

[15] A method for manufacturing a cured encapsulating body having a cured resin film using the adhesive laminate described in any one of the above [1] to [12], comprising the following steps (i) to (iii).

·Process (i): A process of attaching the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate and a support to place an object to be sealed on part of the surface of the sheet (II) for forming a cured resin film.

·Process (ii): A process of covering the surface of the sheet (II) for forming a cured resin film on at least the peripheral portion of the above-mentioned sealing object and the above-mentioned sealing object with a sealing material, thermally curing the sealing material to form a cured sealing body including the above-mentioned sealing object, and simultaneously thermally curing the thermosetting resin layer (Z) to form a cured resin film.

·Process (iii): A process for obtaining a cured encapsulated body having a cured resin film by separating the expandable particles from the interface P through a treatment for expanding the expandable particles.

The adhesive laminate of the present invention can perform a bagging process by fixing a bagging object to a support, and at the same time, can be easily and collectively separated from the support with a weak force after the bagging process.

In addition, by using the above adhesive laminate, a cured encapsulation body having a cured resin film with a flat surface that suppresses warping can be manufactured with improved productivity.

Figure 1 is a cross-sectional schematic diagram of an adhesive laminate showing the configuration of the first form of the adhesive laminate of the present invention.
Figure 2 is a cross-sectional schematic diagram of an adhesive laminate of the second form of the present invention, showing the configuration of the adhesive laminate.
Figure 3 is a cross-sectional schematic diagram of an adhesive laminate showing the configuration of a third form of the adhesive laminate of the present invention.
Fig. 4 is a cross-sectional schematic diagram showing a process for manufacturing a cured encapsulation body having a cured resin film using the adhesive laminate (1a) shown in Fig. 1(a).

In this specification, whether or not the target layer is a "non-inflatable layer" is determined to be a "non-inflatable layer" if, after performing a treatment for expansion for 3 minutes, the volume change rate calculated from the following formula before and after the treatment is less than 5 volume%.

·Volume change rate (%) = {(Volume of the layer after treatment - volume of the layer before treatment) / volume of the layer before treatment} × 100

In addition, as for the “treatment for expansion”, for example, in the case of a layer containing thermally expandable particles, it is good to perform a heat treatment for 3 minutes at the expansion start temperature (t) of the thermally expandable particles.

In this specification, “active ingredient” refers to a component included in the target composition, excluding a dilution solvent.

In this specification, the mass average molecular weight (Mw) is a standard polystyrene conversion value measured by the gel permeation chromatography (GPC) method, and specifically, a value measured based on the method described in the examples.

In this specification, for example, “(meth)acrylic acid” refers to both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.

In this specification, for a preferred numerical range (e.g., a range of content, etc.), the lower and upper limits described stepwise can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60," the "preferable lower limit (10)" and the "more preferable upper limit (60)" can be combined to say "10 to 60."

〔Characteristics of adhesive laminate〕

The adhesive laminate of the present invention comprises a substrate (Y) and an adhesive layer (X), an expandable adhesive sheet (I) including expandable particles in one layer, and a sheet (II) for forming a cured resin film having a thermosetting resin layer (Z), and has a configuration in which the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are directly laminated.

The adhesive laminate of the present invention can be separated at the interface P between the adhesive sheet (I) and the sheet (II) for forming a cured resin film by making one of the layers of the adhesive sheet (I) a layer containing expandable particles and then performing a treatment to expand the expandable particles (hereinafter also referred to as “expansion treatment”).

That is, in the adhesive laminate of the present invention, the expandable particles expand by the expansion treatment, so that the surface of the layer including the expandable particles becomes uneven, thereby reducing the contact area between the adhesive sheet (I) and the sheet (II) for forming a cured resin film. As a result, the adhesive sheet (I) and the sheet (II) for forming a cured resin film can be easily separated at once with a weak force at the interface P.

In addition, the treatment for expanding the expandable particles when separating at interface P is selected according to the type of expandable particles used.

For example, when using thermally expandable particles, heat treatment at a temperature higher than the expansion initiation temperature (t) of the thermally expandable particles is appropriate.

In addition, the adhesive laminate of the present invention comprises a sheet (II) for forming a cured resin film having a thermosetting resin layer (Z), and one surface of the thermosetting resin layer (Z) is configured to be directly laminated with the adhesive sheet (I).

In addition, an object to be sealed is placed on the surface side opposite to the side on which the adhesive sheet (I) of the thermosetting resin layer (Z) is laminated. The object to be sealed may be placed directly on the surface of the other side of the thermosetting resin layer (Z), or may be placed via an adhesive layer provided on the surface of the other side of the thermosetting resin layer (Z).

The adhesive laminate of the present invention is preferably used to form a cured encapsulation body including the encapsulation object by placing the encapsulation object on the surface of the cured resin film forming sheet (II), covering the encapsulation object and at least the peripheral portion of the cured resin film forming sheet (II) with an encapsulation material, and thermally curing the encapsulation material.

In addition, it is more preferable that the adhesive laminate of the present invention be used to obtain a cured encapsulating body having a cured resin film by separating the thermosetting resin layer (Z) from the interface P by a treatment that expands the expandable particles when the encapsulating material is heat-cured to form a cured resin film.

For example, consider a case where a bagging object is placed on the adhesive surface of an adhesive sheet as described in Patent Document 1, the adhesive surface of the bagging object and its surrounding area is covered with a bagging material, and the bagging material is heat-cured to produce a cured bagging body.

When the encapsulating material is heat-cured, a stress is applied that causes the encapsulating material to shrink, but since the adhesive sheet is fixed to the support, the stress in the encapsulating material is suppressed.

However, the cured bag obtained by separating from the support and the adhesive sheet has difficulty in suppressing the stress that tends to shrink. Since the amount of the sealing material is different on the surface side where the sealing target exists and the surface side opposite to it in the cured bag after separation, the shrinkage stress is likely to differ. This difference in shrinkage stress causes warping in the cured bag.

In addition, from the viewpoint of productivity, the cured bag body after heating is usually separated from the support and adhesive sheet while still heated to a certain degree. For this reason, even after separation, as the curing of the bag body progresses, shrinkage also occurs due to natural cooling, making it easier for the cured bag body to warp.

On the other hand, the adhesive laminate of the present invention comprises a sheet (II) for forming a cured resin film having a thermosetting resin layer (Z), and can suppress warping of the cured encapsulation body for the following reasons.

That is, when the sealing target object is placed on the surface of the sheet (II) for forming a cured resin film, covered with a sealing material, and the sealing material is heat-cured, the thermosetting resin layer (Z) is also heat-cured at the same time. At this time, since the thermosetting resin layer (Z) is provided on the surface side of the side where the sealing target object exists, where the amount of the sealing material present is small and the shrinkage stress due to the curing of the sealing material is considered to be small, the shrinkage stress due to the heat-curing of the thermosetting resin layer (Z) acts.

As a result, it is thought that the difference in shrinkage stress between the two surfaces of the cured bag can be reduced, thereby obtaining a cured bag with effectively suppressed warpage.

In addition, the thermosetting resin layer (Z) that contributes to suppressing warping of the cured encapsulation body can be formed into a cured resin film by heat curing. And, by performing the above-described expansion treatment and separating it from the interface P, it is thought that a cured encapsulation body having a cured resin film that suppresses warping and has a flat surface can be manufactured without going through a separate process for forming a cured resin film.

〔Composition of adhesive laminate〕

Figures 1 to 3 are cross-sectional schematic diagrams of adhesive laminates showing the configurations of the adhesive laminates of the first to third embodiments of the present invention. Hereinafter, the configurations of the adhesive laminates shown in Figures 1 to 3, which are embodiments of the present invention, will be described.

In addition, in the adhesive laminates of the first to third forms of the present invention below, a release agent may be further laminated on the adhesive surface of the adhesive layer (X) (or the second adhesive layer (X2)) that is attached to the support, and the surface of the sheet (II) for forming a cured resin film on the opposite side to the adhesive sheet (I).

＜First type of adhesive laminate＞

As an adhesive laminate of the first type of the present invention, an adhesive laminate (1a, 1b) shown in Fig. 1 can be exemplified.

An adhesive laminate (1a, 1b) comprises an adhesive sheet (I) having a substrate (Y) and an adhesive layer (X), and a sheet (II) for forming a cured resin film comprising a thermosetting resin layer (Z), and has a configuration in which the substrate (Y) of the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are directly laminated.

However, the adhesive sheet (I) of the adhesive laminate of the present invention contains expandable particles in one layer.

The adhesive laminate of the first type of the present invention, as shown in Fig. 1, has a substrate (Y) having an expandable substrate layer (Y1) including expandable particles.

As the substrate (Y) having the expandable substrate layer (Y1), it may be a single-layer substrate composed only of the expandable substrate layer (Y1), such as the adhesive laminate (1a) shown in Fig. 1(a), or it may be a multi-layer substrate having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), such as the adhesive laminate (1b) shown in Fig. 1(b).

In the adhesive laminate (1a) shown in Fig. 1(a), the expandable particles included in the expandable base layer (Y1) expand due to the expansion treatment, and the surface of the expandable base layer (Y1) becomes uneven, thereby reducing the contact area with the thermosetting resin layer (Z).

Meanwhile, since the adhesive surface of the adhesive layer (X) is attached so as to be sufficiently closely attached to the support, even if a force that causes unevenness is generated on the surface of the adhesive layer (X) side of the expandable substrate layer (Y1), a repulsive force from the adhesive layer is likely to be generated. For this reason, it is difficult for unevenness to be formed on the surface of the adhesive layer (X) side of the expandable substrate layer (Y1).

As a result, the adhesive laminate (1a) can be easily separated in one go with a weak force at the interface P between the substrate (Y) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film.

In addition, the adhesive layer (X) of the adhesive laminate (1a) can be designed to be more easily separated at the interface P by forming it with an adhesive composition that increases adhesive strength to a support.

In addition, from the viewpoint of suppressing the transfer of stress by the expandable particles to the adhesive layer (X) side, it is preferable that the substrate (Y) has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), as in the adhesive laminate (1b) shown in Fig. 1(b).

The stress caused by the expansion of the expandable particles of the expandable substrate layer (Y1) is hardly transmitted to the adhesive layer (X) because it is suppressed by the non-expandable substrate layer (Y2).

For this reason, the adhesion of the adhesive layer (X) to the support can be maintained well without change before and after the expansion treatment.

In addition, as in the adhesive laminate (1b) shown in Fig. 1(b), it is preferable to have a configuration in which the expandable substrate layer (Y1) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are directly laminated, and the adhesive layer (X) is laminated on the surface of the non-expandable substrate layer (Y2).

＜Second type adhesive laminate＞

As an adhesive laminate of the second type of the present invention, an adhesive laminate (2a, 2b) shown in Fig. 2 can be exemplified.

The adhesive laminate (2a, 2b) has a configuration in which the adhesive layer (X) of the adhesive sheet (I) is composed of a first adhesive layer (X1) and a second adhesive layer (X2), a substrate (Y) is sandwiched between the first adhesive layer (X1) and the second adhesive layer (X2), and the adhesive surface of the first adhesive layer (X1) is directly laminated with a thermosetting resin layer (Z).

In addition, in the adhesive laminate of the second form of the present invention, the adhesive surface of the second adhesive layer (X2) is attached to a support.

In the second form of the adhesive laminate of the present invention, it is also preferable that the substrate (Y) has an expandable substrate layer (Y1) containing expandable particles.

As the substrate (Y) having the expandable substrate layer (Y1), it may be a single-layer substrate composed only of the expandable substrate layer (Y1), such as the adhesive laminate (2a) shown in Fig. 2(a), or it may be a multi-layer substrate having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), such as the adhesive laminate (2b) shown in Fig. 2(b).

However, from the viewpoint of forming an adhesive laminate that maintains good adhesion between the second adhesive layer (X2) and the support before and after the expansion treatment as described above, it is preferable that the substrate (Y) has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2).

In addition, in the adhesive laminate of the second form of the present invention, when using a substrate (Y) having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), it is preferable to have a configuration in which a first adhesive layer (X1) is laminated on the surface of the expandable substrate layer (Y1) and a second adhesive layer (X2) is laminated on the surface of the non-expandable substrate layer (Y2), as shown in Fig. 2(b).

In the second form of the adhesive laminate of the present invention, the expandable particles in the expandable substrate layer (Y1) constituting the substrate (Y) expand through expansion treatment, thereby forming unevenness on the surface of the expandable substrate layer (Y1).

In addition, since the first adhesive layer (X1) is also pushed up by the unevenness formed on the surface of the inflatable substrate layer (Y1), and unevenness is also formed on the adhesive surface of the first adhesive layer (X1), the contact area between the first adhesive layer (X1) and the thermosetting resin layer (Z) decreases.

As a result, by the expansion treatment, the first adhesive layer (X1) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film can be easily separated at the interface P with a weak force.

In addition, in the second form of the adhesive laminate of the present invention, from the viewpoint of making the adhesive laminate easily and collectively separable with a weaker force at the interface P, it is preferable that the adhesive sheet (I) has a configuration in which the expandable substrate layer (Y1) of the substrate (Y) and the first adhesive layer (X1) are directly laminated.

＜Third type adhesive laminate＞

As a third type of adhesive laminate of the present invention, an adhesive laminate (3) shown in Fig. 3 can be exemplified.

The adhesive laminate (3) shown in Fig. 3 has an adhesive sheet (I) having, on one surface side of a substrate (Y), a first adhesive layer (X1) which is an expandable adhesive layer containing expandable particles, and on the other surface side of the substrate (Y), a second adhesive layer (X2) which is a non-expandable adhesive layer, and has a configuration in which the first adhesive layer (X1) and a thermosetting resin layer (Z) of a sheet (II) for forming a cured resin film are directly laminated.

In the adhesive laminate (3), the adhesive surface of the second adhesive layer (X2) is attached to a support.

In addition, it is preferable that the substrate (Y) of the adhesive laminate of the third form of the present invention is composed of a non-expandable substrate layer.

In the adhesive laminate of the third form of the present invention, by expansion treatment, the expandable particles in the first adhesive layer (X1), which is an expandable adhesive layer, expand, so that unevenness is created on the surface of the first adhesive layer (X1), thereby reducing the contact area between the first adhesive layer (X1) and the thermosetting resin layer (Z).

Meanwhile, the surface of the substrate (Y) side of the first adhesive layer (X1) is unlikely to have unevenness because the substrate (Y) is laminated.

For this reason, by the expansion treatment, unevenness is easily formed on the surface of the thermosetting resin layer (Z) side of the first adhesive layer (X1), and as a result, the first adhesive layer (X1) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film can be easily separated at once with a weak force at the interface P.

〔Various properties of adhesive laminate〕

One form of the adhesive laminate of the present invention can be easily and collectively separated with a weak force at the interface P between the adhesive sheet (I) and the sheet for forming a cured resin film (II) by expansion treatment.

Here, in one form of the adhesive laminate of the present invention, after the thermosetting resin layer (Z) is thermosetted to form a cured resin film, the peeling force (F 1 ) when separating at the interface P of the cured resin film formed by curing the thermosetting resin layer (Z) of the adhesive sheet (I) and the cured resin film-forming sheet ( _II ) by expansion treatment is usually 0 to 2000 mN/25 mm, preferably 0 to 1000 mN/25 mm, more preferably 0 to 500 mN/25 mm, still more preferably 0 to 150 mN/25 mm, still more preferably 0 to 100 mN/25 mm, and still more preferably 0 to 50 mN/25 mm.

In cases where the peeling force (F ₁ ) is 0 mN/25 mm, even if the peeling force is measured by the method described in the examples, there are also cases where the peeling force is too small to be measured.

In addition, from the viewpoint of sufficiently fixing the bagging object and not adversely affecting the bagging operation before the thermal curing and expansion treatment of the thermosetting resin layer (Z), it is preferable that the adhesion between the adhesive sheet (I) and the thermosetting resin layer (Z) of the cured resin film forming sheet (II) be high.

From the above viewpoint, in one form of the adhesive laminate of the present invention, before thermal curing of the thermosetting resin layer (Z) and before performing the expansion treatment, the peeling force (F ₀ ) when separating at the interface P between the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, still more preferably 160 mN/25 mm or more, and further preferably 50000 mN/25 mm or less.

In one form of the adhesive laminate of the present invention, the ratio of peel strength (F ₁ ) to peel strength (F ₀ ) [(F ₁ )/(F ₀ )] is preferably 0 to 0.9, more preferably 0 to 0.8, still more preferably 0 to 0.5, and still more preferably 0 to 0.2.

Peeling strength (F ₁ ) and peeling strength (F ₀ ) refer to values measured based on the method described in the examples.

In addition, when measuring the peeling force (F ₁ ), the temperature condition should be higher than the expansion initiation temperature (t) of the thermally expandable particles when using thermally expandable particles.

In addition, the temperature condition for measuring the peeling force (F ₀ ) is preferably lower than the expansion initiation temperature (t) of the thermally expandable particles when using thermally expandable particles, but is basically room temperature (23°C).

In one form of the adhesive laminate of the present invention, the adhesive strength of the adhesive layer (X) (the first adhesive layer (X1) and the second adhesive layer (X2)) of the adhesive sheet (I) at room temperature (23°C) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm, still more preferably 0.4 to 6.0 N/25 mm, and still more preferably 0.5 to 4.0 N/25 mm.

When the adhesive sheet (I) has a first adhesive layer (X1) and a second adhesive layer (X2), it is preferable that the adhesive strengths of the first adhesive layer (X1) and the second adhesive layer (X2) are each within the above range, but from the viewpoint of improving adhesion to the support and enabling easier separation at the interface P, it is more preferable that the adhesive strength of the second adhesive layer (X2) attached to the support is higher than the adhesive strength of the first adhesive layer (X1).

In addition, in one form of the adhesive laminate of the present invention, from the viewpoint of improving adhesion with the object to be sealed, it is preferable that the surface of the sheet (II) for forming a cured resin film, on the side where the object to be sealed is placed, has adhesiveness.

Specifically, the adhesive strength of the surface of the sheet (II) for forming a cured resin film at room temperature (23°C) on the side where the sealing target is placed is preferably 0.01 to 5 N/25 mm, more preferably 0.05 to 4 N/25 mm, and even more preferably 0.1 to 3 N/25 mm.

Here, in the case where the sheet (II) for forming a cured resin film is composed only of a thermosetting resin layer (Z), it is preferable that the adhesive strength of the surface of the thermosetting resin layer (Z) be adjusted to be within the above range.

In addition, when the sheet (II) for forming a cured resin film has a thermosetting resin layer (Z) and an adhesive layer, it is preferable that the adhesive strength of the adhesive layer be adjusted to be within the above range.

In addition, in this specification, such adhesive strength means a value measured according to the method described in the examples.

The substrate (Y) of the adhesive sheet (I) is a non-adhesive substrate.

In the present invention, the determination of whether or not the substrate is a non-adhesive substrate is made by determining that, for the surface of the target substrate, if the probe tack value measured in accordance with JIS Z0237: 1991 is less than 50 mN/5 mmφ, the substrate is judged to be a “non-adhesive substrate.”

The probe tack value on the surface of the substrate (Y) of the adhesive sheet (I) used in one embodiment of the present invention is each independently usually less than 50 mN/5 mmφ, preferably less than 30 mN/5 mmφ, more preferably less than 10 mN/5 mmφ, and even more preferably less than 5 mN/5 mmφ.

In addition, in this specification, the probe tack value on the surface of the substrate means a value measured according to the method described in the examples.

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

[Composition of adhesive sheet (I)]

The adhesive sheet (I) of the adhesive laminate of the present invention is an expandable adhesive sheet having a substrate (Y) and an adhesive layer (X), and including expandable particles in one of the layers.

In a case where a layer including expandable particles is included in the composition of the substrate (Y) and in a case where it is included in the composition of the adhesive layer (X), the adhesive sheet (I) used in one embodiment of the present invention is divided into the following forms.

· First type of adhesive sheet (I): An adhesive sheet (I) having a substrate (Y) having an expandable substrate layer (Y1) containing expandable particles.

·Second type adhesive sheet (I): An adhesive sheet (I) having, on both sides of a substrate (Y), a first adhesive layer (X1) which is an expandable adhesive layer containing expandable particles, and a second adhesive layer (X2) which is a non-expandable adhesive layer.

＜First type of adhesive sheet (I)＞

As a first type of adhesive sheet (I), as shown in Figs. 1 and 2, an example is one in which the substrate (Y) has an expandable substrate layer (Y1) containing expandable particles.

In the first type of adhesive sheet (I), from the viewpoint of enabling easy and unitary separation with a weak force at the interface P, it is preferable that the adhesive layer (X) is a non-expandable adhesive layer.

Specifically, in the adhesive sheet (I) of the adhesive laminate (1a, 1b) shown in Fig. 1, it is preferable that the adhesive layer (X) is a non-expandable adhesive layer.

In addition, in the adhesive sheet (I) of the adhesive laminate (2a, 2b) shown in Fig. 2, it is preferable that both the first adhesive layer (X1) and the second adhesive layer (X2) are non-expandable adhesive layers.

The thickness of the substrate (Y) before the expansion treatment of the adhesive sheet (I) of the first form is preferably 10 to 1000 µm, more preferably 20 to 700 µm, further preferably 25 to 500 µm, and still more preferably 30 to 300 µm.

The thickness of the adhesive layer (X) before the expansion treatment of the adhesive sheet (I) of the first form is preferably 1 to 60 µm, more preferably 2 to 50 µm, further preferably 3 to 40 µm, and still more preferably 5 to 30 µm.

In addition, in the present specification, for example, as shown in FIG. 2, when the adhesive sheet (I) has a plurality of adhesive layers, the “thickness of the adhesive layer (X)” means the thickness of each adhesive layer (in FIG. 2, the thickness of each of the adhesive layers (X1) and (X2)).

In addition, in this specification, the thickness of each layer constituting the adhesive laminate means a value measured according to the method described in the examples.

In the adhesive sheet (I) of the first form, before the expansion treatment, the thickness ratio [(Y1)/(X)] of the expandable substrate layer (Y1) and the adhesive layer (X) is preferably 1000 or less, more preferably 200 or less, further preferably 60 or less, and still more preferably 30 or less.

When the above thickness ratio is 1000 or less, an adhesive laminate can be formed that can be easily and collectively separated with a weak force at the interface P of the adhesive sheet (I) and the sheet for forming a cured resin film (II) by expansion treatment.

In addition, the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1.0 or more, and even more preferably 5.0 or more.

In addition, in the adhesive sheet (I) of the first form, the substrate (Y) may be composed only of the expandable substrate layer (Y1) as shown in Fig. 1(a), or may have the expandable substrate layer (Y1) on the side of the sheet (II) for forming a cured resin film as shown in Fig. 1(b) and the non-expandable substrate layer (Y2) on the side of the adhesive layer (X).

In the adhesive sheet (I) of the first form, before the expansion treatment, the thickness ratio [(Y1)/(Y2)] of the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) is preferably 0.02 to 200, more preferably 0.03 to 150, and even more preferably 0.05 to 100.

＜Second type adhesive sheet (I)＞

As an adhesive sheet (I) of the second type, as shown in Fig. 3, there may be mentioned one having, on both sides of the substrate (Y), a first adhesive layer (X1) which is an expandable adhesive layer containing expandable particles, and a second adhesive layer (X2) which is a non-expandable adhesive layer.

In addition, in the second type of adhesive sheet (I), the first adhesive layer (X1), which is an expandable adhesive layer, and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are in direct contact.

In addition, in the adhesive sheet (I) of the second type, the substrate (Y) is preferably a non-expandable substrate. The non-expandable substrate is preferably composed only of a non-expandable substrate layer (Y2).

In the adhesive sheet (I) of the second form, before the expansion treatment, the thickness ratio [(X1)/(X2)] of the first adhesive layer (X1) which is an expandable adhesive layer and the second adhesive layer (X2) which is a non-expandable adhesive layer is preferably 0.1 to 80, more preferably 0.3 to 50, and even more preferably 0.5 to 15.

In addition, in the adhesive sheet (I) of the second form, before the expansion treatment, the thickness ratio [(X1)/(Y1)] of the first adhesive layer (X1), which is an expandable adhesive layer, and the substrate (Y) is preferably 0.05 to 20, more preferably 0.1 to 10, and even more preferably 0.2 to 3.

Hereinafter, the expandable particles included in one layer constituting the adhesive sheet (I) will be described, and then the expandable substrate layer (Y1), the non-expandable substrate layer (Y2), and the adhesive layer (X) constituting the substrate (Y) will be described in detail.

＜Expandable Particles＞

The expandable particles used in the present invention may be particles that expand through a predetermined expansion treatment.

The average particle diameter of the expandable particles used in one embodiment of the present invention before expansion at 23°C is preferably 3 to 100 μm, more preferably 4 to 70 μm, further preferably 6 to 60 μm, and still more preferably 10 to 50 μm.

In addition, the average particle size of the expandable particles before expansion is the median volume particle size ( _D50 ), and means the particle size at which the cumulative volume frequency calculated with the smaller particle size of the expandable particles before expansion corresponds to 50% in the particle distribution of the expandable particles before expansion measured using a laser diffraction particle size distribution measuring device (e.g., product name “MASTERSIZER 3000” manufactured by Malvern).

The 90% particle diameter ( _D90 ) before expansion at 23°C of the expandable particles used in one embodiment of the present invention is preferably 10 to 150 μm, more preferably 20 to 100 μm, further preferably 25 to 90 μm, and still more preferably 30 to 80 μm.

In addition, the 90% particle diameter ( _D90 ) of the expandable particles before expansion means the particle diameter at which the cumulative volume frequency calculated with the smaller particle diameter of the expandable particles before expansion corresponds to 90% in the particle distribution of the expandable particles before expansion, as measured using a laser diffraction particle size distribution measuring device (e.g., MASTERSIZER 3000 manufactured by Malvern).

The expandable particles used in one embodiment of the present invention are preferably thermally expandable particles that expand by heat treatment at a temperature higher than the expansion initiation temperature (t).

The heat-expandable particles used in one embodiment of the present invention may be particles having an expansion initiation temperature (t) higher than the curing temperature of the encapsulating material and not expanding when the encapsulating material is cured. Specifically, it is preferable that the heat-expandable particles be particles having an expansion initiation temperature (t) adjusted to 60 to 270°C.

Additionally, the expansion initiation temperature (t) is appropriately selected depending on the curing temperature of the encapsulating material used.

In addition, in this specification, the expansion initiation temperature (t) of the thermally expandable particles means a value measured based on the following method.

(Method for measuring the expansion start temperature (t) of thermally expandable particles)

A sample is prepared by adding 0.5 mg of the thermally expandable particles to be measured to an aluminum cup with a diameter of 6.0 mm (inner diameter of 5.65 mm) and a depth of 4.8 mm and placing an aluminum lid (diameter of 5.6 mm and thickness of 0.1 mm) on top.

Using a dynamic viscoelasticity measuring device, the height of the sample is measured from the top of the aluminum lid while a force of 0.01 N is applied to the sample with a pressurizer. Then, while a force of 0.01 N is applied to the sample with the pressurizer, the sample is heated from 20°C to 300°C at a heating rate of 10°C/min, and the displacement in the vertical direction of the pressurizer is measured, and the temperature at which the displacement in the positive direction begins is taken as the expansion initiation temperature (t).

As the heat-expandable particle, a microencapsulated foaming agent is preferably formed of an outer shell made of a thermoplastic resin and an encapsulated component enclosed in the outer shell and vaporized when heated to a predetermined temperature.

Thermoplastic resins forming the outer shell of the microencapsulated foaming agent include, for example, vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, etc.

The inclusion components included in the outer shell include, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexyl cyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, isotridecane, 4-methyl dodecane, isotetradecane, isopentadecane, isohexadecane, 2, 2, 4, 4, 6, 8, 8-heptamethylnonane, isoheptadecane, Examples thereof include isooctadecane, isononadecane, 2, 6, 10, 14-tetramethylpentadecane, cyclotridecane, heptyl cyclohexane, n-octyl cyclohexane, cyclopentadecane, nonyl cyclohexane, decyl cyclohexane, pentadecyl cyclohexane, hexadecyl cyclohexane, heptadecyl cyclohexane, and octadecyl cyclohexane.

These included ingredients may be used alone, or two or more may be used in combination.

The expansion initiation temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of inclusion component.

The maximum volume expansion ratio of the heat-expandable particles used in one embodiment of the present invention when heated to a temperature higher than the expansion initiation temperature (t) is preferably 1.5 to 100 times, more preferably 2 to 80 times, further preferably 2.5 to 60 times, and still more preferably 3 to 40 times.

＜Inflatable substrate layer (Y1)＞

The expandable substrate layer (Y1) of the adhesive sheet (I) used in one embodiment of the present invention is a layer that contains expandable particles and can be expanded by a predetermined expansion treatment.

The content of expandable particles in the expandable substrate layer (Y1) is preferably 1 to 40 mass%, more preferably 5 to 35 mass%, further preferably 10 to 30 mass%, and even more preferably 15 to 25 mass%, with respect to the total mass (100 mass%) of the expandable substrate layer (Y1).

In addition, from the viewpoint of improving the interlayer adhesion between the intumescent substrate layer (Y1) and other layers laminated therewith, surface treatment by an oxidation method or a roughening method, adhesive treatment, or primer treatment may be performed on the surface of the intumescent substrate layer (Y1).

Examples of oxidation methods include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, and examples of roughening methods include sand blasting and solvent treatment.

In one embodiment of the present invention, the expandable substrate layer (Y1) is preferably a heat-expandable substrate layer containing heat-expandable particles, and it is more preferable that the heat-expandable substrate layer satisfies the following requirement (1).

·Requirement (1): The storage elastic modulus E'(t) of the thermally expandable base layer at the expansion initiation temperature (t) of the thermally expandable particles is 1.0×10 ⁷ Pa or less.

In addition, in this specification, the storage elastic modulus E' of the thermally expandable substrate layer at a given temperature means a value measured according to the method described in the examples.

The above requirement (1) can be said to be an indicator of the rigidity of the thermally expandable base layer immediately before the thermally expandable particles expand.

In order to enable easy separation with a weak force at the interface P of the adhesive sheet (I) and the sheet (II) for forming a cured resin film, it is necessary to easily form unevenness on the surface of the side laminated with the thermosetting resin layer (Z) of the adhesive sheet (I) when heated to a temperature higher than the expansion initiation temperature (t).

That is, in the heat-expandable base material layer satisfying the above requirement (1), the heat-expandable particles expand and become sufficiently large at the expansion initiation temperature (t), so that unevenness is easily formed on the surface of the adhesive sheet (I) on the side where the thermosetting resin layer (Z) is laminated.

As a result, an adhesive laminate can be formed that can be easily separated with a weak force at the interface P between the adhesive sheet (I) and the sheet for forming a cured resin film (II).

The storage elastic modulus E'(t) of the heat-expandable substrate layer as stipulated in requirement (1) is, from the above viewpoint, preferably 9.0×10 ⁶ Pa or less, more preferably 8.0×10 ⁶ Pa or less, further preferably 6.0×10 ⁶ Pa or less, still more preferably 4.0×10 ⁶ Pa or less, and still more preferably 1.0×10 ⁶ Pa or less.

In addition, from the viewpoint of suppressing the flow of expanded heat-expandable particles, improving the shape retention of the unevenness formed on the surface of the adhesive sheet (I) on the side where the thermosetting resin layer (Z) is laminated, and enabling easier separation with a weak force at the interface P, the storage elastic modulus E'(t) of the heat-expandable base material layer specified in requirement (1) is preferably 1.0×10 ³ Pa or more, more preferably 1.0×10 ⁴ Pa or more, and even more preferably 1.0×10 ⁵ Pa or more.

It is preferable that the expandable base layer (Y1) be formed of a resin composition (y) containing resin and expandable particles.

In addition, the resin composition (y) may contain a base additive as needed, within a range that does not impair the effects of the present invention.

Examples of additives for use in the composition include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-blocking agents, and colorants.

Additionally, these additives for substrates may be used alone or in combination of two or more.

When containing such substrate additives, the content of each substrate additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, per 100 parts by mass of the resin.

As for the expandable particles included in the resin composition (y), which is the forming material of the expandable base layer (Y1), they are as described above, and are preferably heat-expandable particles.

The content of the expandable particles is preferably 1 to 40 mass%, more preferably 5 to 35 mass%, further preferably 10 to 30 mass%, and even more preferably 15 to 25 mass%, relative to the total amount (100 mass%) of the effective ingredient of the resin composition (y).

The resin included in the resin composition (y), which is a forming material of the expandable base layer (Y1), may be either a non-adhesive resin or an adhesive resin.

That is, even if the resin included in the resin composition (y) is an adhesive resin, in the process of forming the expandable base layer (Y1) from the resin composition (y), the adhesive resin undergoes a polymerization reaction with a polymerizable compound, so that the obtained resin becomes a non-adhesive resin, and the expandable base layer (Y1) including the resin becomes non-adhesive.

The mass average molecular weight (Mw) of the resin included in the resin composition (y) is preferably 10 million to 1,000,000, more preferably 10 million to 700,000, and even more preferably 10 million to 500,000.

In addition, when the resin is a copolymer having two or more types of structural units, the form of the copolymer is not particularly limited, and may be any one of a block copolymer, a random copolymer, and a graft copolymer.

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

In addition, from the viewpoint of forming an expandable base layer (Y1) satisfying the above requirement (1), it is preferable that the resin included in the resin composition (y) includes at least one selected from an acrylic urethane resin and an olefin resin.

In addition, among the acrylic urethane resins, the following resin (U1) is preferable.

·Acrylic urethane resin (U1) formed by polymerizing a vinyl compound containing a urethane prepolymer (UP) and a (meth)acrylic acid ester.

(Acrylic urethane resin (U1))

As a urethane prepolymer (UP) that becomes the main chain of an acrylic urethane resin (U1), a reaction product of a polyol and a polyvalent isocyanate can be mentioned.

In addition, it is preferable that the urethane prepolymer (UP) be obtained by further performing a chain extension reaction using a chain extender.

Examples of polyols that are raw materials for urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, ester amide type polyols, ester/ether type polyols, carbonate type polyols, etc.

These polyols may be used alone or in combination of two or more.

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

Examples of ester-type diols include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentane diol, neopentyl glycol, and 1,6-hexanediol; alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; Examples of the polymer include a condensation polymer with one or more compounds selected from diols such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenyl methane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hetonic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methyl hexahydrophthalic acid, and one or more compounds selected from dicarboxylic acids and anhydrides thereof.

Specifically, examples thereof include 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-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, and polyneopentyl terephthalate diol.

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

Examples of carbonate-type diols include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, 1,3-propylene carbonate diol, 2,2-dimethyl propylene carbonate diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, etc.

Polyisocyanates that are raw materials for urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

These polyisocyanates may be used alone or in combination of two or more.

In addition, these polyvalent isocyanates may be trimethylolpropane adduct-type modified products, water-reacted biuret-type modified products, or isocyanurate-type modified products containing an isocyanurate ring.

Among these, as the polyisocyanate used in one embodiment of the present invention, diisocyanate is preferable, and at least one selected from 4,4'-diphenyl methane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate is more preferable.

Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and the like, but isophorone diisocyanate (IPDI) is preferred.

In one embodiment of the present invention, the urethane prepolymer (UP) that becomes the main chain of the acrylic urethane resin (U1) is preferably a straight-chain urethane prepolymer that is a reaction product of a diol and a diisocyanate and has an ethylenically unsaturated group at both terminals.

As a method for introducing an ethylenically unsaturated group to both terminals of the above-mentioned straight-chain urethane prepolymer, an example of which is a method of reacting an NCO group at the terminal of a straight-chain urethane prepolymer formed by reacting a diol and a diisocyanate compound with a hydroxyalkyl (meth)acrylate can be mentioned.

Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.

The vinyl compound that becomes the side chain of the acrylic urethane resin (U1) contains at least (meth)acrylic acid ester.

As the (meth)acrylic acid ester, at least one selected from alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate is preferable, and it is more preferable to use alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate in combination.

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

The number of carbon atoms in the alkyl group of the above 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.

In addition, examples of the hydroxyalkyl (meth)acrylate include the hydroxyalkyl (meth)acrylate used to introduce ethylenically unsaturated groups to both terminals of the linear urethane prepolymer described above.

Examples of vinyl compounds other than (meth)acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, α-methyl styrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; and polar group-containing monomers such as vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinyl pyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta(acrylamide).

These can 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 mass%, more preferably 65 to 100 mass%, further preferably 80 to 100 mass%, and even more preferably 90 to 100 mass%, with respect to the total amount (100 mass%) of the vinyl compound.

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

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

(olefin resin)

An olefin-based resin suitable as a resin included in the resin composition (y) is a polymer having at least a structural unit derived from an olefin monomer.

As the above olefin monomer, an α-olefin having 2 to 8 carbon atoms is preferable, and specific examples thereof include ethylene, propylene, butylene, isobutylene, and 1-hexene.

Among these, ethylene and propylene are preferred.

Specific olefin resins include, for example, ultra-low-density polyethylene (VLDPE, density: 880 kg/㎥ or more and less than 910 kg/㎥), low-density polyethylene (LDPE, density: 910 kg/㎥ or more and less than 915 kg/㎥), medium-density polyethylene (MDPE, density: 915 kg/㎥ or more and less than 942 kg/㎥), high-density polyethylene (HDPE, density: 942 kg/㎥ or more), linear low-density polyethylene, etc.; polypropylene resin (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); olefin terpolymers such as ethylene-propylene-(5-ethylidene-2-norbornene); etc.

In one embodiment of the present invention, the olefin resin may be a modified olefin resin that has undergone at least one modification selected from acid modification, hydroxyl modification, and acrylic modification.

For example, as an acid-modified olefin resin produced by carrying out acid modification on an olefin resin, an example of a modified polymer produced by graft polymerizing an unsaturated carboxylic acid or its anhydride onto the above-described unmodified olefin resin can be mentioned.

Examples of the above unsaturated carboxylic acids or anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride.

In addition, unsaturated carboxylic acids or their anhydrides may be used alone or in combination of two or more.

As an acrylic-modified olefin resin produced by performing acrylic modification on an olefin resin, an example of a modified polymer produced by graft polymerizing an alkyl (meth)acrylate as a side chain to the above-described unmodified olefin resin as a main chain can be exemplified.

The number of carbon atoms in the alkyl group of the above alkyl (meth)acrylate is preferably 1 to 20, more preferably 1 to 16, and even more preferably 1 to 12.

As the above alkyl (meth)acrylate, examples thereof include compounds that can be selected as the monomer (a1') described below.

As a hydroxyl-modified olefin resin produced by carrying out hydroxyl group modification on an olefin resin, an example thereof is a modified polymer produced by graft polymerizing a hydroxyl group-containing compound onto the above-described unmodified olefin resin as the main chain.

Examples of the above hydroxyl group-containing compounds include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol;

(Resins other than acrylic urethane resins and olefin resins)

In one embodiment of the present invention, the resin composition (y) may contain a resin other than an acrylic urethane resin and an olefin resin, within a range that does not impair the effects of the present invention.

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; triacetate cellulose; polycarbonate; polyurethanes other than acrylic urethane resins; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; fluorine resins, and the like.

However, from the viewpoint of forming an expandable base layer (Y1) that satisfies the above requirement (1), it is preferable that the content ratio of resins other than acrylic urethane resin and olefin resin in the resin composition (y) be small.

The content ratio of resin other than acrylic urethane resin and olefin resin is preferably less than 30 parts by mass, more preferably less than 20 parts by mass, more preferably less than 10 parts by mass, even more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass, with respect to 100 parts by mass of the total amount of resin contained in the resin composition (y).

(Dance-type resin composition (y1))

As a resin composition (y) used in one embodiment of the present invention, an example is a solvent-free resin composition (y1) which is formed by blending 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 expandable particles described above, and does not blend a solvent.

In the non-solvent type resin composition (y1), no solvent is mixed, but the energy ray polymerizable monomer contributes to the improvement of the reversibility of the oligomer.

For a film formed with a non-woven resin composition (y1), it is easy to form an expandable base layer (Y1) that satisfies the above requirement (1) by irradiating it with energy rays.

In addition, the type, shape, and mixing amount (content) of the expandable particles blended in the non-woven resin composition (y1) are as described above.

The mass average molecular weight (Mw) of the oligomer included in the non-woven resin composition (y1) is 50,000 or less, but is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, still more preferably 3,000 to 35,000, and still more preferably 4,000 to 30,000.

In addition, as the above oligomer, any resin included in the resin composition (y) described above that has an ethylenically unsaturated group and a mass average molecular weight of 50,000 or less is preferable, but the above-described urethane prepolymer (UP) is preferable.

In addition, as the above oligomer, a modified olefin resin having an ethylenically unsaturated group can also be used.

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

Examples of the energy-ray polymerizable monomer include alicyclic polymerizable compounds such as isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, cyclohexyl (meth)acrylate, adamantane (meth)acrylate, and tricyclodecane acrylate; aromatic polymerizable compounds such as phenyl hydroxypropyl acrylate, benzyl acrylate, and phenol ethylene oxide-modified acrylate; and heterocyclic polymerizable compounds such as tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinyl pyrrolidone, and N-vinyl caprolactam.

These energy-ray polymerizable monomers may be used alone or in combination of two or more.

The mixing ratio of the above oligomer and the energy ray polymerizable monomer (the above oligomer/energy ray polymerizable monomer) is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, and even more preferably 35/65 to 80/20.

In one embodiment of the present invention, it is preferable that the non-solvent type resin composition (y1) further comprises a photopolymerization initiator.

By containing a photopolymerization initiator, the curing reaction can be sufficiently promoted by irradiation with relatively low-energy energy rays.

Examples of photopolymerization initiators include 1-hydroxy-cyclohexylphenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethyl thiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, 8-chloroanthraquinone, and the like.

These photopolymerization initiators may be used alone or in combination of two or more.

The amount of the photopolymerization initiator to be blended is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, and even more preferably 0.02 to 3 parts by mass, relative to the total amount (100 parts by mass) of the oligomer and energy ray polymerizable monomer.

＜Non-inflatable substrate layer (Y2)＞

Examples of the forming material of the non-expandable substrate layer (Y2) constituting the substrate (Y) include paper, resin, metal, etc., and can be appropriately selected depending on the intended use of one type of adhesive laminate of the present invention.

Examples of paper materials include thin-leaf paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, sulfur-acid paper, and glassine paper.

Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; triacetate cellulose; polycarbonate; urethane resins such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; fluorine resins, etc.

Metals include, for example, aluminum, tin, chromium, and titanium.

These forming materials may be composed of one type, or may be used in combination of two or more types.

As a non-expandable substrate layer (Y2) using two or more types of forming materials, examples thereof include a laminate of paper material with a thermoplastic resin such as polyethylene, or a metal film formed on the surface of a resin film or sheet containing resin.

In addition, as a method for forming a metal layer, examples thereof include a method of depositing the metal by a PVD method such as vacuum deposition, sputtering, or ion plating, or a method of attaching a metal foil made of the metal using a general adhesive.

In addition, from the viewpoint of improving the interlayer adhesion between the non-expandable substrate layer (Y2) and other layers laminated, when the non-expandable substrate layer (Y2) contains resin, surface treatment by an oxidation method or a roughening method, adhesion treatment, or primer treatment may be performed on the surface of the non-expandable substrate layer (Y2), similarly to the above-described expandable substrate layer (Y1).

In addition, when the non-expandable substrate layer (Y2) contains a resin, it may contain the above-described substrate additive that can also be contained in the resin composition (y) together with the resin.

The non-intumescent substrate layer (Y2) is a non-intumescent layer determined based on the method described above.

For this reason, the volume change rate (%) of the non-expandable substrate layer (Y2) calculated from the above formula is less than 5 volume%, but is preferably less than 2 volume%, more preferably less than 1 volume%, even more preferably less than 0.1 volume%, and even more preferably less than 0.01 volume%.

In addition, the non-expandable substrate layer (Y2) may contain expandable particles as long as the volume change rate is within the above range. For example, even if expandable particles are contained, the volume change rate can be adjusted to the above range by selecting the resin included in the non-expandable substrate layer (Y2).

However, the smaller the content of expandable particles in the non-expandable substrate layer (Y2), the more desirable it is.

The content of specific expandable particles is usually less than 3 mass%, preferably less than 1 mass%, more preferably less than 0.1 mass%, further preferably less than 0.01 mass%, and even more preferably less than 0.001 mass%, with respect to the total mass (100 mass%) of the non-expandable substrate layer (Y2).

＜Adhesive layer (X)＞

The adhesive layer (X) of the adhesive sheet (I) used in one embodiment of the present invention can be formed from an adhesive composition (x) containing an adhesive resin.

In addition, the adhesive composition (x) may contain, if necessary, an adhesive additive such as a crosslinking agent, a tackifier, a polymerizable compound, or a polymerization initiator.

Below, each component included in the adhesive composition (x) is described.

In addition, even when the adhesive sheet (I) has a first adhesive layer (X1) and a second adhesive layer (X2), the first adhesive layer (X1) and the second adhesive layer (X2) can also be formed using an adhesive composition (x) containing each component shown below.

(adhesive resin)

The adhesive resin used in one embodiment of the present invention may be a polymer that has adhesiveness alone and has a mass average molecular weight (Mw) of 10,000 or more.

The mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and even more preferably 30,000 to 1 million, from the viewpoint of improving adhesive strength.

Specific adhesive resins include, for example, rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based resins.

These adhesive resins may be used alone or in combination of two or more types.

In addition, when the adhesive resin is a copolymer having two or more types of structural units, the form of the copolymer is not particularly limited, and may be any one of a block copolymer, a random copolymer, and a graft copolymer.

The adhesive resin used in one embodiment of the present invention may be an energy ray-curable adhesive resin having a polymerizable functional group introduced into the side chain of the adhesive resin.

By forming an adhesive layer using a composition containing an energy ray-curable adhesive resin, the adhesive strength can be reduced by irradiating the energy ray.

Examples of the polymerizable functional group include a (meth)acryloyl group, a vinyl group, etc.

Also, as energy rays, ultraviolet rays or electron rays can be mentioned, but ultraviolet rays are preferable.

In addition, as a material for forming an adhesive layer capable of reducing adhesive strength by irradiating energy rays, a composition containing a monomer or oligomer having a polymerizable functional group may be used.

It is preferable that such compositions further contain a photopolymerization initiator.

In one embodiment of the present invention, from the viewpoint of exhibiting excellent adhesive strength, it is preferable that the adhesive resin contains an acrylic resin.

In addition, when using an adhesive sheet (I) having a first adhesive layer (X1) and a second adhesive layer (X2), since the first adhesive layer (X1) in contact with the sheet (II) for forming a cured resin film contains an acrylic resin, it is easy to form unevenness on the surface of the first adhesive layer.

The content ratio of the acrylic resin in the adhesive resin is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, further preferably 70 to 100 mass%, and even more preferably 85 to 100 mass%, relative to the total amount (100 mass%) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X).

The content of the adhesive resin is preferably 35 to 100 mass%, more preferably 50 to 100 mass%, further preferably 60 to 98 mass%, and even more preferably 70 to 95 mass%, relative to the total amount (100 mass%) of the effective ingredient of the adhesive composition (x) or the total mass (100 mass%) of the adhesive layer (X).

(Bridger)

In one embodiment of the present invention, when the adhesive composition (x) contains an adhesive resin having a functional group, it is preferable to further contain a crosslinking agent.

The above crosslinking agent reacts with an adhesive resin having a functional group to crosslink the adhesive resins using the functional group as a crosslinking starting point.

Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, and metal chelate crosslinking agents.

These cross-linkers may be used alone or in combination of two or more.

Among these cross-linking agents, isocyanate-based cross-linking agents are preferable from the viewpoints of increasing cohesion and improving adhesiveness, and ease of acquisition.

The content of the crosslinking agent is appropriately adjusted depending on the number of functional groups possessed by the adhesive resin, but is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and even more preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the adhesive resin having functional groups.

(adhesive agent)

In one embodiment of the present invention, the adhesive composition (x) may further contain a tackifier from the viewpoint of further improving adhesive strength.

In this specification, the term “tackifier” refers to a component that auxiliary improves the adhesive strength of the above-described adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, and is distinct from the above-described adhesive resin.

The mass average molecular weight (Mw) of the adhesive agent is preferably 400 to 10,000, more preferably 500 to 8,000, and even more preferably 800 to 5,000.

Examples of the tackifier include rosin-based resins, terpene-based resins, styrene-based resins, C5-based petroleum resins obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene produced by the thermal decomposition of petroleum naphtha, C9-based petroleum resins obtained by copolymerizing C9 fractions such as indene and vinyl toluene produced by the thermal decomposition of petroleum naphtha, and hydrogenated resins obtained by hydrogenating these.

The softening point of the adhesive is preferably 60 to 170°C, more preferably 65 to 160°C, and even more preferably 70 to 150°C.

In addition, in this specification, the “softening point” of the tackifier means a value measured in accordance with JIS K 2531.

The adhesive may be used alone, or two or more types with different softening points or structures may be used in combination.

In addition, when using two or more types of multiple tackifiers, it is preferable that the weighted average of the softening points of these multiple tackifiers falls within the above range.

The content of the adhesive agent is preferably 0.01 to 65 mass%, more preferably 0.1 to 50 mass%, further preferably 1 to 40 mass%, and even more preferably 2 to 30 mass%, relative to the total amount (100 mass%) of the effective ingredient of the adhesive composition (x) or the total mass (100 mass%) of the adhesive layer (X).

(Photopolymerization initiator)

In one embodiment of the present invention, when the adhesive composition (x) is an energy ray-curable composition and includes an energy ray-curable adhesive resin, or a monomer or oligomer having a polymerizable functional group, it is preferable that the composition further contains a photopolymerization initiator.

By containing a photopolymerization initiator, the curing reaction can be sufficiently promoted by irradiation with relatively low-energy energy rays.

In addition, as a photopolymerization initiator, the same ones as those incorporated in the solvent-free resin composition (y1) described above can be 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 even more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of the monomer or oligomer having a polymerizable functional group.

(additive for adhesive)

In one embodiment of the present invention, the adhesive composition (x) may contain, in addition to the additives described above, an additive for an adhesive used in a general adhesive, within a range that does not impair the effects of the present invention.

Examples of such adhesive additives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, and antistatic agents.

Additionally, these adhesive additives may be used alone or in combination of two or more.

When containing such adhesive additives, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, per 100 parts by mass of the adhesive resin.

In addition, when using the adhesive sheet (I) of the second type described above having the first adhesive layer (X1) which is an expandable adhesive layer, the forming material of the first adhesive layer (X1) which is an expandable adhesive layer is formed of an expandable adhesive composition (x11) which further contains expandable particles in the adhesive composition (x) described above.

The above expandable particles are as described above.

The content of the expandable particles is preferably 1 to 70 mass%, more preferably 2 to 60 mass%, further preferably 3 to 50 mass%, and even more preferably 5 to 40 mass%, relative to the total amount (100 mass%) of the effective ingredient of the expandable adhesive composition (x11) or the total mass (100 mass%) of the expandable adhesive layer.

Meanwhile, when the adhesive layer (X) is a non-expandable adhesive layer, it is preferable that the content of expandable particles in the adhesive composition, which is a forming material of the non-expandable adhesive layer, be very small.

The content of expandable particles in the adhesive composition (x), which is a material for forming a non-expandable adhesive layer, is preferably less than 1 mass%, more preferably less than 0.1 mass%, further preferably less than 0.01 mass%, and even more preferably less than 0.001 mass%, relative to the total amount (100 mass%) of the effective ingredient of the adhesive composition (x) or the total mass (100 mass%) of the adhesive layer (X).

In addition, when using an adhesive sheet (I) having a first adhesive layer (X1) and a second adhesive layer (X2), which are non-expandable adhesive layers, such as the adhesive laminate (2a, 2b) shown in Fig. 2, the storage shear modulus G' (23) of the first adhesive layer (X1), which is a non-expandable adhesive layer, at 23°C is preferably 1.0×10 ⁸ Pa or less, more preferably 5.0×10 ⁷ Pa or less, even more preferably 1.0×10 ⁷ Pa or less.

If the storage shear modulus G'(23) of the first adhesive layer (X1) which is a non-expandable adhesive layer is 1.0×10 ⁸ Pa or less, then, for example, in the case of a configuration such as the adhesive laminate (2a, 2b) shown in Fig. 2, unevenness is likely to be formed on the surface of the first adhesive layer (X1) which is in contact with the sheet (II) for forming a cured resin film due to expansion of the expandable particles in the expandable base material layer (Y1) by the expansion treatment.

As a result, an adhesive laminate can be formed that can be easily and collectively separated with a weak force at the interface P of the adhesive sheet (I) and the sheet for forming a cured resin film (II).

In addition, the storage shear modulus G'(23) of the first adhesive layer (X1), which is a non-expandable adhesive layer at 23°C, is preferably 1.0×10 ⁴ Pa or more, more preferably 5.0×10 ⁴ Pa or more, and even more preferably 1.0×10 ⁵ Pa or more.

[Composition of sheet (II) for forming a cured resin film]

The sheet (II) for forming a cured resin film of the adhesive laminate of the present invention has a thermosetting resin layer (Z).

The sheet (II) for forming a cured resin film used in one embodiment of the present invention may have a single-layer configuration consisting solely of a thermosetting resin layer (Z), or may have a multi-layer configuration in which another layer is provided on one surface side of the thermosetting resin layer (Z).

However, in the sheet (II) for forming a cured resin film used in one embodiment of the present invention, another layer may be provided on one surface side of the thermosetting resin layer (Z), but on the other surface side of the thermosetting resin layer (Z), another layer is not provided and is directly laminated with the adhesive sheet (I).

Here, in the sheet (II) for forming a cured resin film used in one embodiment of the present invention, an adhesive layer may be further provided on one surface side of the thermosetting resin layer (Z), and further, a non-thermosetting substrate layer may be provided between the thermosetting resin layer (Z) and the adhesive layer.

The above-described adhesive layer can be formed using an adhesive composition (x) which is a forming material of the above-described adhesive layer (X). In addition, the above-described non-thermosetting substrate layer can also be formed using the same forming material as the above-described non-expandable substrate layer (Y2).

Below, the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film is described.

＜Thermosetting resin layer (Z)＞

The thermosetting resin layer (Z) may be formed of a composition capable of forming a cured resin film by thermosetting. However, from the viewpoint of producing an adhesive laminate capable of producing a cured encapsulated body having a cured resin film that suppresses warping and has a flat surface, it is preferable that the layer be formed of a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B).

In addition, the thermosetting composition (z) may further contain one or more selected from a colorant (C), a coupling agent (D), and an inorganic filler (E), but from the above viewpoint, it is preferable to contain at least an inorganic filler (E).

The thickness of the thermosetting resin layer (Z) is preferably 1 to 500 ㎛, more preferably 5 to 300 ㎛, further preferably 10 to 200 ㎛, and even more preferably 15 to 100 ㎛.

From the viewpoint of producing an adhesive laminate capable of producing a cured encapsulated body having a cured resin film having a flat surface by suppressing warping, the storage elastic modulus E' of the cured resin film formed by heat-curing the thermosetting resin layer (Z) at 23°C is preferably 1.0×10 ⁷ Pa or more, more preferably 1.0×10 ⁸ Pa or more, further preferably 1.0×10 ⁹ Pa or more, further preferably 5.0×10 ⁹ Pa or more, and further preferably 1.0×10 ¹³ Pa or less, more preferably 1.0×10 ¹² Pa or less, further preferably 5.0×10 ¹¹ Pa or less, further preferably 1.0×10 ¹¹ Pa or less.

Below, various components included in the thermosetting composition (z), which is a forming material of the thermosetting resin layer (Z), are described.

(Polymer component (A))

The polymer component (A) included in the thermosetting composition (z) means a compound having a mass average molecular weight of 20,000 or more and at least one type of repeating unit.

By including a polymerizable component (A) in the thermosetting resin layer (Z) formed, flexibility and film-forming properties can be imparted to the thermosetting resin layer (Z), thereby improving the sheet property retention.

The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3 million, still more preferably 50,000 to 2 million, still more preferably 100,000 to 1.5 million, and still more preferably 200,000 to 1 million.

The content of component (A) is preferably 5 to 50 mass%, more preferably 8 to 40 mass%, and even more preferably 10 to 30 mass%, relative to the total amount (100 mass%) of the effective components of the thermosetting composition (z) or the total mass (100 mass%) of the thermosetting resin layer (Z).

Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber polymers, etc.

These polymer components (A) may be used alone or in combination of two or more.

In addition, in this specification, an acrylic polymer having an epoxy group or a phenoxy resin having an epoxy group is thermosetting, but if they are a compound having a mass average molecular weight of 20,000 or more and at least one type of repeating unit, they are included in the concept of a polymer component (A).

Among these, it is preferable that the polymer component (A) contains an acrylic polymer (A1).

The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100 mass%, more preferably 70 to 100 mass%, further preferably 80 to 100 mass%, and even more preferably 90 to 100 mass%, with respect to the total amount (100 mass%) of the polymer component (A).

(Acrylic polymer (A1))

The mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3 million, more preferably 100,000 to 1.5 million, further preferably 150,000 to 1.2 million, and still more preferably 250,000 to 1 million, from the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer (Z).

The glass transition temperature (Tg) of the acrylic polymer (A1) is preferably -60 to 50°C, more preferably -50 to 30°C, even more preferably -40 to 10°C, and still more preferably -35 to 5°C, from the viewpoint of imparting good adhesion to the surface of the thermosetting resin layer (Z) and improving the reliability of a cured encapsulation body having a cured resin film manufactured using the adhesive laminate.

As the acrylic polymer (A1), a polymer having an alkyl (meth)acrylate as a main component can be exemplified, and specifically, an acrylic polymer including a structural unit (a1) derived from an alkyl (meth)acrylate (a1') having an alkyl group having 1 to 18 carbon atoms (hereinafter also referred to as a "monomer (a1')") is preferable, and an acrylic copolymer including a structural unit (a2) derived from a functional group-containing monomer (a2') (hereinafter also referred to as a "monomer (a2')") together with the structural unit (a1) is more preferable.

Acrylic polymer (A1) may be used alone or in combination of two or more types.

In addition, when the acrylic polymer (A1) is a copolymer, the form of the copolymer may be any one of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

The number of carbon atoms in the alkyl group of the monomer (a1') is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, from the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer (Z). The alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.

These monomers (a1') may be used alone or in combination of two or more.

From the viewpoint of improving the reliability of a cured encapsulating body having a cured resin film manufactured using an adhesive laminate, it is preferable that the monomer (a1') contains an alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms, and it is more preferable that it contains methyl (meth)acrylate.

From the above viewpoint, the content of the structural unit (a11) derived from an alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms is preferably 1 to 80 mass%, more preferably 5 to 80 mass%, and even more preferably 10 to 80 mass%, with respect to the precursor unit (100 mass%) of the acrylic polymer (A1).

In addition, from the viewpoint of increasing the gloss value of the cured resin film formed by heat-curing the thermosetting resin layer (Z) and improving the laser marking suitability, it is preferable that the monomer (a1') contains an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms, more preferably an alkyl (meth)acrylate having an alkyl group having 4 to 6 carbon atoms, and even more preferably butyl (meth)acrylate.

From the above viewpoint, the content of the structural unit (a12) derived from an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms (preferably 4 to 6, more preferably 4) is preferably 1 to 70 mass%, more preferably 5 to 65 mass%, and even more preferably 10 to 60 mass%, with respect to the precursor unit (100 mass%) of the acrylic polymer (A1).

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

As the monomer (a2'), at least one selected from a hydroxyl group-containing monomer and an epoxy group-containing monomer is preferable.

In addition, the monomer (a2') may be used alone or in combination of two or more types.

As the hydroxyl group-containing monomer, examples thereof include the hydroxyl group-containing compounds described above, with hydroxyalkyl (meth)acrylate being preferable and 2-hydroxyethyl (meth)acrylate being more preferable.

Examples of the epoxy-containing monomers include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, (3,4-epoxycyclohexyl) methyl (meth)acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth)acrylate; glycidyl crotonate, and allyl glycidyl ether.

Among these, as the epoxy-containing monomer, an epoxy group-containing (meth)acrylate is preferable, and glycidyl (meth)acrylate is more preferable.

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

In addition, the acrylic polymer (A1) may have a structural unit derived from a monomer other than the structural units (a1) and (a2) described above, as long as the effects of the present invention are not impaired.

Other monomers include, for example, vinyl acetate, styrene, ethylene, and α-olefins.

＜Thermosetting component (B)＞

The thermosetting component (B) is responsible for thermosetting the thermosetting resin layer (Z) and forming a hard cured resin film, and is a compound having a mass average molecular weight of less than 20,000.

The mass average molecular weight (Mw) of the curable component (B) is preferably 10,000 or less, more preferably 100 to 10,000.

From the viewpoint of producing an adhesive laminate capable of producing a cured encapsulated body having a cured resin film having a flat surface by suppressing warping, the thermosetting component (B) preferably includes an epoxy compound (B1) that is a compound having an epoxy group and a thermosetting agent (B2), and it is more preferable to further include a curing accelerator (B3) together with the epoxy compound (B1) and the thermosetting agent (B2).

Examples of the epoxy compound (B1) include epoxy compounds having two or more functional groups in the molecule and a mass average molecular weight of less than 20,000, such as multifunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene-type epoxy resins, biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and phenylene skeleton-type epoxy resins.

Epoxy compounds (B1) may be used alone or in combination of two or more types.

From the viewpoint of producing an adhesive laminate capable of producing a cured encapsulating body having a cured resin film having a flat surface by suppressing warping, the content of the epoxy compound (B1) is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, further preferably 10 to 150 parts by mass, and still more preferably 20 to 120 parts by mass, relative to 100 parts by mass of the polymer component (A).

The thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1).

As a thermosetting agent, a compound having two or more functional groups capable of reacting with an epoxy group per molecule is preferable.

Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Among these, from the viewpoint of producing an adhesive laminate capable of producing a cured encapsulating body having a cured resin film that suppresses warping and has a flat surface, 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 even more preferable.

Examples of phenolic thermosetting agents having a phenol group include multifunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-type phenol resins, xylok-type phenol resins, and aralkyl phenol resins.

Examples of amine-based heat curing agents having an amino group include dicyandiamide (DICY).

These thermosetting agents (B2) may be used alone or in combination of two or more.

From the viewpoint of producing an adhesive laminate capable of producing a cured encapsulated body having a cured resin film having a flat surface by suppressing warping, the content of the heat curing agent (B2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, per 100 parts by mass of the epoxy compound (B1).

A curing accelerator (B3) is a compound that has the function of increasing the speed of thermal curing when thermally curing a thermosetting resin layer (Z).

Examples of the curing accelerator (B3) include tertiary amines such as triethylenediamine, benzyl dimethyl amine, triethanol amine, dimethyl aminoethanol, and tris (dimethyl aminomethyl) phenol; imidazoles such as 2-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 2-phenyl-4,5-dihydroxy methyl imidazole, and 2-phenyl-4-methyl-5-hydroxy methyl imidazole; organic phosphines such as tributylphosphine, diphenyl phosphine, and triphenyl phosphine; and tetraphenyl boron salts such as tetraphenylphosphoniumtetraphenylborate and triphenyl phosphine tetraphenyl borate.

These hardening accelerators (B13) may be used alone or in combination of two or more types.

From the viewpoint of producing an adhesive laminate having a cured encapsulated body having a cured resin film having a flat surface by suppressing warping, the content of the curing accelerator (B3) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and even more preferably 0.3 to 4 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (B1) and the heat curing agent (B2).

＜Colorant (C)＞

The thermosetting composition (z) used in one embodiment of the present invention may further contain a colorant (C).

A thermosetting resin layer (Z) formed from a thermosetting composition (z) containing a coloring agent (C) can, when thermosetting to form a cured resin film, shield infrared rays and the like generated from a surrounding device and prevent malfunction of a sealing target (semiconductor chip, etc.).

As a coloring agent (C), organic or inorganic pigments and dyes can be used.

Any dye can be used as the dye, for example, an acid dye, a reactive dye, a direct dye, a disperse dye, or a cationic dye.

In addition, as a pigment, there is no particular limitation and it can be appropriately selected and used from known pigments.

Among these, black pigment is preferable from the viewpoint of having good shielding properties against electromagnetic waves and infrared rays and further improving identification according to the laser marking method.

Examples of black pigments include carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon, but carbon black is preferable from the viewpoint of increasing the reliability of semiconductor chips.

Additionally, these colorants (C) may be used alone or in combination of two or more.

The content of component (C) is preferably 0.1 to 30 mass%, more preferably 0.5 to 25 mass%, further preferably 1.0 to 15 mass%, and even more preferably 1.2 to 5 mass%, relative to the total amount (100 mass%) of the effective components of the thermosetting composition (z) or the total mass (100 mass%) of the thermosetting resin layer (Z).

＜Coupling agent (D)＞

The thermosetting composition (z) used in one embodiment of the present invention may further contain a coupling agent (D).

A thermosetting resin layer (Z) formed from a thermosetting composition (z) containing a coupling agent (D) can improve adhesion to a sealing target. In addition, for a cured resin film formed by thermosetting the thermosetting resin layer (Z), water resistance can be improved without impairing heat resistance.

As the coupling agent (D), a compound that reacts with a functional group of component (A) or component (B) is preferable, and specifically, a silane coupling agent is preferable.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(methacryloxypropyl)trimethoxysilane, 3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxy silyl propyl)tetrasulfane, methyltrimethoxysilane, Examples include methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, and imidazole silane.

These coupling agents (D) may be used alone or in combination of two or more.

The molecular weight of the coupling agent (D) is preferably 100 to 15,000, more preferably 125 to 10,000, more preferably 150 to 5,000, more preferably 175 to 3,000, and still more preferably 200 to 2,000.

The content of component (D) is preferably 0.01 to 10 mass%, more preferably 0.05 to 7 mass%, further preferably 0.10 to 4 mass%, and still more preferably 0.15 to 2 mass%, relative to the total amount (100 mass%) of the effective components of the thermosetting composition (z) or the total mass (100 mass%) of the thermosetting resin layer (Z).

＜Weapon Refill (E)＞

From the viewpoint of producing an adhesive laminate capable of producing a cured encapsulated body having a cured resin film having a flat surface by suppressing warping, the thermosetting composition (z) used in one embodiment of the present invention preferably further contains an inorganic filler (E).

A thermosetting resin layer (Z) formed of a thermosetting composition (z) containing an inorganic filler (E) can adjust the degree of thermosetting of the thermosetting resin layer (Z) so that the difference in shrinkage stress between two surfaces of the cured encapsulating body is reduced when the encapsulating material is thermosetted. As a result, a cured encapsulating body having a cured resin film with a flat surface that suppresses warping can be obtained.

In addition, the coefficient of thermal expansion of the cured resin film formed by heat-curing the thermosetting resin layer (Z) can be adjusted to an appropriate range, and the reliability of the sealing target can be improved. In addition, the moisture absorption rate of the cured resin film can also be reduced.

As the inorganic filler (E), it is preferable that it be non-expandable, and examples thereof include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, spherical beads of these, non-heat-expandable particles such as single crystal fibers, and glass fibers.

These weapon fillers (E) can be used alone or in combination of two or more.

Among these, silica or alumina is preferable from the viewpoint of being an adhesive laminate capable of producing a cured encapsulating body having a cured resin film with a flat surface that suppresses warping.

The average particle size of the inorganic filler (E) is preferably 0.3 to 50 µm, more preferably 0.5 to 30 µm, and even more preferably 0.7 to 10 µm from the viewpoint of improving the gloss value of the cured resin film formed by thermosetting the formed thermosetting resin layer (Z).

From the viewpoint of producing an adhesive laminate capable of producing a cured encapsulated body having a cured resin film having a flat surface by suppressing warping, the content of component (E) is preferably 25 to 80 mass%, more preferably 30 to 70 mass%, further preferably 40 to 65 mass%, and still more preferably 45 to 60 mass%, relative to the total amount (100 mass%) of the effective components of the thermosetting composition (z) or the total mass (100 mass%) of the thermosetting resin layer (Z).

＜Other additives＞

The thermosetting composition (z) used in one embodiment of the present invention may contain additives other than the components (A) to (E) described above, as long as the effects of the present invention are not impaired.

Other additives may include, for example, crosslinking agents, leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, and chain transfer agents.

However, the total content of additives other than components (A) to (E) is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 5 mass%, with respect to the total amount (100 mass%) of the effective ingredients of the thermosetting composition (z) or the total mass (100 mass%) of the thermosetting resin layer (Z).

〔How to use the adhesive laminate〕

The adhesive laminate of the present invention can fix a bagging object to a support and perform bagging processing, and at the same time, can be easily separated from the support with a weak force after bagging processing. In addition, by using the adhesive laminate, a cured bagging body having a cured resin film with a flat surface that suppresses warping can be manufactured with improved productivity.

For this reason, the adhesive laminate of the present invention,

Place the bagging object on the surface of the sheet (II) for forming a cured resin film,

A method of use is preferable, which comprises covering the surface of the above-mentioned bagging object and at least the periphery of the above-mentioned bagging object, the sheet (II) for forming a cured resin film, with a bagging material, and thermally curing the bagging material to form a cured bagging body including the above-mentioned bagging object.

In addition, in the above-described method of use, when curing the encapsulating material, it is preferable to use it so that the thermosetting resin layer (Z) is also thermosetted to form a cured resin film, and at the same time, the expandable particles are separated from the interface P by a treatment that expands them, thereby obtaining a cured encapsulating body having a cured resin film.

As described above, by using the adhesive laminate of the present invention, a cured encapsulating body having a cured resin film having a flat surface with suppressed warping can be manufactured with improved productivity.

In addition, in the above-described method of use, the suitable composition of the adhesive laminate is as described above, and the type of the encapsulating material, the method of covering the encapsulating material, all conditions of thermal curing, etc. are as described in the section of “Method for producing a cured encapsulating body having a cured resin film” shown below.

〔Method for manufacturing a cured encapsulated body having a cured resin film〕

As a method for manufacturing a cured encapsulating body having a cured resin film using the adhesive laminate of the present invention, a method having the following steps (i) to (iii) can be exemplified.

·Process (i): A process of attaching the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate and a support to place an object to be sealed on part of the surface of the sheet (II) for forming a cured resin film.

·Process (ii): A process of covering the surface of the sheet (II) for forming a cured resin film on at least the peripheral portion of the above-mentioned sealing object and the above-mentioned sealing object with a sealing material, thermally curing the sealing material to form a cured sealing body including the above-mentioned sealing object, and simultaneously thermally curing the thermosetting resin layer (Z) to form a cured resin film.

·Process (iii): A process for obtaining a cured encapsulated body having a cured resin film by separating the expandable particles from the interface P through a treatment for expanding the expandable particles.

Fig. 4 is a cross-sectional schematic diagram showing a process for manufacturing a cured encapsulation body having a cured resin film using the adhesive laminate (1a) shown in Fig. 1(a). Hereinafter, each of the above-described processes will be described with appropriate reference to Fig. 4.

＜Fairness (i)＞

Process (i) is a process of attaching the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate and a support to place an object to be sealed on part of the surface of the sheet (II) for forming a cured resin film.

Fig. 4(a) shows a state in which, in this process, the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) is attached to a support (50) using an adhesive laminate (1a), and a sealing target object (60) is placed on a part of the surface of the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film.

In addition, Fig. 4(a) shows an example using the adhesive laminate (1a) shown in Fig. 1(a), but even when using the adhesive laminate of the present invention having a different configuration, the support, the adhesive laminate, and the bagging object are similarly laminated or placed in this order.

As for the temperature conditions in process (i), it is preferable that it be carried out at a temperature at which the expandable particles do not expand.

For example, when using a thermally expandable particle as an expandable particle, it is preferable that the temperature be lower than the expansion initiation temperature (t) of the thermally expandable particle, but it is preferable that the temperature be lower than the expansion initiation temperature (t) of the thermally expandable particle.

It is preferable that the above support be attached to the entire surface of the adhesive surface of the adhesive layer (X) of the adhesive laminate.

Therefore, it is preferable that the support be plate-shaped. In addition, it is preferable that the surface area of the support on the side to be attached to the adhesive surface of the adhesive layer (X) is greater than the area of the adhesive surface of the adhesive layer (X), as shown in Fig. 4.

The material constituting the above support is appropriately selected after considering the required characteristics, such as mechanical strength and heat resistance, depending on the type of the bagging target object or the type of bagging material used in process (ii).

Materials constituting a specific support include, for example, metallic materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; resin materials such as epoxy resin, ABS resin, acrylic resin, engineering plastic, super engineering plastic, polyimide resin, and polyamideimide resin; and composite materials such as glass epoxy resin. Among these, SUS, glass, and silicon wafers are preferable.

Other 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 above support is appropriately selected depending on the type of the bagging target object, the type of bagging material used in process (ii), etc., but is preferably 20 ㎛ or more and 50 mm or less, and more preferably 60 ㎛ or more and 20 mm or less.

Meanwhile, examples of the sealing target placed on a part of the surface of the sheet (II) for forming a cured resin film include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, panel substrates, etc.

For example, when the packaging target is a semiconductor chip, a semiconductor chip having a cured resin film can be manufactured by using the adhesive laminate of the present invention.

Semiconductor chips can be made of conventionally known materials, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface.

And, it is preferable that the semiconductor chip be placed so that the back side opposite to the circuit surface is covered with the surface of the sheet (II) for forming a cured resin film. In this case, after placement, the circuit surface of the semiconductor chip is exposed.

For bonding semiconductor chips, known devices such as Flip Chip Bonder and die bonder can be used.

The layout of the semiconductor chip arrangement, the number of arrangements, etc. should be appropriately determined according to the type of package intended for the purpose, the number of productions, etc.

Here, it is desirable to apply it to a package in which a semiconductor chip is covered with an encapsulating material over an area larger than the chip size, such as FOWLP, FOPLP, etc., and a redistribution layer is formed not only on the circuit surface of the semiconductor chip but also on the surface area of the encapsulating material.

For this reason, the semiconductor chip is placed on a part of the surface of the sheet (II) for forming a cured resin film, and it is preferable that a plurality of semiconductor chips are placed on the surface in a state of being aligned at a constant interval, and it is more preferable that a plurality of semiconductor chips are placed on the surface in a state of being aligned in a matrix of multiple rows and multiple columns at a constant interval.

The spacing between semiconductor chips can be appropriately determined depending on the type of package being used.

＜Fair Process (ii)＞

Process (ii) is a process of covering the surface of the sheet (II) for forming a cured resin film, including the sealing object and at least the peripheral portion of the sealing object, with a sealing material (hereinafter also referred to as “covering treatment”), thermally curing the sealing material (hereinafter also referred to as “thermosetting treatment”), thereby forming a cured sealing body including the sealing object, and simultaneously thermally curing the thermosetting resin layer (Z) to form a cured resin film.

In the covering treatment of process (ii), first, at least the peripheral portion of the surface of the sealing target object and the sheet (II) for forming a cured resin film is covered with a sealing material.

The encapsulating material covers the entire exposed surface of the encapsulating object and is also filled into the gaps between multiple semiconductor chips.

For example, Fig. 4(b) shows a state in which the surfaces of the bagging target (60) and the sheet (II) for forming a cured resin film are covered with a bagging material.

A bagging material has the function of protecting the bagging object and its associated elements from the external environment.

The encapsulating material used in the manufacturing method of the present invention is a thermosetting encapsulating material containing a thermosetting resin.

In addition, the sealing material may be in a solid form such as granules, pellets, or films at room temperature, or may be in a liquid form in the form of a composition, but from the viewpoint of workability, a film-shaped sealing material, that is, a sealing resin film, is preferable.

As a covering method, any of the methods applied in the conventional bagging process can be appropriately selected and applied depending on the type of bagging material, and examples thereof include a roll lamination method, a vacuum press method, a vacuum lamination method, a spin coat method, a die coat method, a transfer molding method, and a compression molding method.

Then, after performing the covering treatment, the encapsulating material is heat-cured to obtain a cured encapsulating body in which the encapsulating object is encapsulated by the encapsulating material.

In addition, the covering treatment and heat curing treatment of process (ii) are preferably performed at a temperature at which the expandable particles do not expand, and for example, when using an adhesive laminate having a layer including heat-expandable particles, it is preferable to perform the treatment under a temperature condition lower than the expansion initiation temperature (t) of the heat-expandable particles.

In addition, the covering process and the heat-curing process may be performed separately, but when the sealing material is heated in the covering process, the sealing material may be heat-cured as is by the heating, and the covering process and the heat-curing process may be performed simultaneously.

In this process, simultaneously with the heat curing treatment of the encapsulating material, the thermosetting resin layer (Z) is also heat cured to form a cured resin film.

In the manufacturing method of the present invention, as shown in Fig. 4(b), a thermosetting resin layer (Z) is installed on the side of a bagging object (60) sealed with a bagging material (70), and a thermosetting treatment is performed.

Since the thermosetting resin layer (Z) is installed, it is thought that the difference in shrinkage stress between the two surfaces of the resulting cured bag can be reduced, so that warping occurring in the cured bag can be effectively suppressed.

＜Process (iii)＞

Process (iii) is a process of obtaining a cured encapsulated body having a cured resin film by separating the expandable particles from the interface P through a treatment that expands them.

Figure 4(c) shows a state in which the expandable particles are separated from the interface P by a process for expanding them.

As shown in Fig. 4(c), by separating at the interface P, a cured encapsulation body (80) in which a sealing target (60) is encapsulated and a cured resin film (Z') in which a thermosetting resin layer (Z) is thermosetted can be obtained, thereby obtaining a cured encapsulation body (100) having a cured resin film.

In addition, the presence of the cured resin film (Z') has the function of effectively suppressing warping occurring in the cured bag, while protecting the bagged object, thereby contributing to improving the reliability of the bagged object.

The “expanding treatment” in process (iii) is performed depending on the type of expandable particles being used.

For example, when using thermally expandable particles, by heating to a temperature higher than the thermal expansion initiation temperature (t), the thermally expandable particles are expanded, thereby creating unevenness on the surface of the adhesive sheet (I) on the sheet (II) side for forming a cured resin film. As a result, they can be easily separated in one go with a weak force at the interface P.

When expanding the thermally expandable particles, the “temperature higher than the expansion initiation temperature (t)” is preferably higher than “expansion initiation temperature (t) + 10°C” and lower than “expansion initiation temperature (t) + 60°C,” and more preferably higher than “expansion initiation temperature (t) + 15°C” and lower than “expansion initiation temperature (t) + 40°C.”

In addition, from the viewpoint of making it easy to separate at the interface P between the adhesive sheet (I) and the sheet for forming the cured resin film (II), it is preferable that the heat source during heating be installed on the support side.

The cured encapsulation body having the cured resin film thus obtained may then undergo a process such as grinding the cured encapsulation body until the circuit surface of the semiconductor chip is exposed, performing rewiring on the circuit surface, forming an external electrode pad, and connecting the external electrode pad and the external terminal electrode.

In addition, after an external terminal electrode is connected to the hardened bag body, it can be separated to manufacture a semiconductor device.

Example

In the present invention, the following examples will be described in detail, but the present invention is not limited to the following examples. In addition, the physical properties in the following manufacturing examples and examples are values measured according to the following methods.

＜Mass average molecular weight (Mw)＞

A gel permeation chromatograph (TOSOH CORPORATION, product name “HLC-8020”) was used to measure under the following conditions, and the values measured in standard polystyrene conversion were used.

(Measurement conditions)

·Column: 「TSK guard column HXL-L」 「TSK gel G2500HXL」 「TSK gel G2000HXL」 「TSK gel G1000HXL」 (all made by TOSOH CORPORATION) connected in sequence

·Column temperature: 40℃

·Developing solvent: Tetrahydrofuran

·Flow rate: 1.0mL/min

＜Measurement of thickness of each layer＞

Measurement was made using a static pressure thickness gauge manufactured by Teclock Co., Ltd. (Product number: “PG-02J”, standard specifications: compliant with JIS K6783, Z1702, Z1709).

＜Storage elastic modulus E＇ of the intumescent substrate layer (Y1)＞

The formed expandable substrate layer (Y1) was made into a test sample with a size of 5 mm in length × 30 mm in width × 200 ㎛ in thickness, and the release agent was removed.

Using a dynamic viscoelasticity measuring device (TA Instruments, product name “DMAQ800”), the storage elastic modulus E’ of the test sample at a specified temperature was measured under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, a frequency of 1 Hz, and an amplitude of 20 μm.

＜Storage shear modulus G' of adhesive layers (X1) and (X2)＞

The formed adhesive layers (X1) and (X2) were cut into circles with a diameter of 8 mm, the release agent was removed, and the layers were laminated to a thickness of 3 mm to serve as test samples.

Using a viscoelasticity measuring device (Anton Paar, device name: "MCR300"), the storage shear modulus G' of the test sample at a specified temperature was measured according to the torsional shear method under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, and a frequency of 1 Hz.

＜Storage elastic modulus E＇ of the cured resin film after heat curing of the thermosetting resin layer (Z)＞

After laminating the thermosetting resin layer (Z) to a thickness of 200 μm, the layer was placed in an oven under an air atmosphere and heated at 130°C for 2 hours to heat the 200 μm thick thermosetting resin layer (Z) to form a cured resin film.

Using a dynamic viscoelasticity measuring device (TA Instruments, product name “DMAQ800”), the storage elastic modulus E’ of the cured resin film formed at 23°C was measured under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, a frequency of 11 Hz, and an amplitude of 20 μm.

<Probe Tack Value>

The material to be measured was cut into a square with a side size of 10 mm, and then left to stand for 24 hours in an environment of 23°C and 50% RH (relative humidity), which was used as a test sample.

In an environment of 23℃ and 50%RH (relative humidity), a probe tack tester (TESTER SANGYO CO,. LTD., product name “TE-6001”) was used to measure the probe tack value on the surface of the test sample in accordance with JIS Z0237: 1991.

Specifically, a probe of a stainless steel product having a diameter of 5 mm was brought into contact with the surface of a test sample for 1 second at a contact load of 0.98 N/cm2, and then the force required to remove the probe from the surface of the test sample at a speed of 10 mm/sec was measured, and the obtained value was taken as the probe tack value of the test sample.

＜Measurement of adhesive strength＞

A PET film (manufactured by TOYOBO CO., LTD., product name “Cosmo Shine A4100”) having a thickness of 50 ㎛ was laminated on the surface of an adhesive layer or a thermosetting resin layer (Z) formed on a release film.

Then, the peeling film was removed, and the surface of the exposed adhesive layer or thermosetting resin layer (Z) was attached to a stainless steel plate (SUS304, No. 360 polished) as an adherend, and after leaving it in an environment of 23°C and 50%RH (relative humidity) for 24 hours, the adhesive strength at 23°C was measured at a tensile speed of 300 mm/min according to the 180° peeling method based on JIS Z0237:2000 in the same environment.

Manufacturing Example 1 (Synthesis of urethane prepolymer)

In a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solid content ratio) of polycarbonate diol having a mass average molecular weight of 1,000 was mixed with isophorone diisocyanate such that the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of isophorone diisocyanate was 1/1, 160 parts by mass of toluene was further added, and under a nitrogen atmosphere, with stirring, the mixture was reacted at 80°C for 6 hours or more until the isocyanate group concentration reached the theoretical amount.

Next, a solution of 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) diluted with 30 parts by mass of toluene was added, and the mixture was reacted at 80°C for an additional 6 hours until the isocyanate groups at both ends disappeared, thereby obtaining a urethane prepolymer having a mass average molecular weight of 29,000.

Manufacturing Example 2 (Synthesis of acrylic urethane resin)

In a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solid content) of the urethane prepolymer obtained in Manufacturing Example 1, 117 parts by mass (solid content) of methyl methacrylate (MMA), 5.1 parts by mass (solid content) of 2-hydroxyethyl methacrylate (2-HEMA), 1.1 parts by mass (solid content) of 1-thioglycerol, and 50 parts by mass of toluene were added, stirred, and the temperature was increased to 105°C.

Then, in the reaction vessel, a solution of 2.2 parts by mass (solid content ratio) of a radical initiator (product name: "ABN-E" manufactured by Japan Finechem Inc.) diluted with 210 parts by mass of toluene was added dropwise over 4 hours while maintaining the temperature at 105°C.

After completion of loading, the reaction was performed at 105°C for 6 hours to obtain a solution of an acrylic urethane resin having a mass average molecular weight of 105,000.

Manufacturing Example 3 (Preparation of thermosetting composition)

Each component of the type and mixing amount shown below (all “effective ingredient ratio”) was mixed, further diluted with methyl ethyl ketone, and stirred uniformly to prepare a solution of a curable composition having a solid content concentration (effective ingredient concentration) of 61 mass%.

·Acrylic polymer: Blending amount = 26.07 parts by mass

An acrylic polymer (mass average molecular weight: 400,000, glass transition temperature: -1°C) obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate, equivalent to the above component (A1).

·Epoxy compound (1): Mixing amount = 10.4 parts by mass

Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828", epoxy equivalent = 184 to 194 g/eq), equivalent to the above component (B1).

·Epoxy compound (2): Mixing amount = 5.2 parts by mass

Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, product name “EPICLON HP－7200 HH”, epoxy equivalent = 255 to 260 g/eq), equivalent to the above component (B1).

·Epoxy compound (3): Mixing 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 (B1).

·Thermosetting agent: Mixing amount = 0.42 parts by mass

Dicyandiamide (manufactured by ADEKA, product name “ADEKA HARDNA EH－3636 AS”, active hydrogen content = 21 g/eq), equivalent to the above component (B2).

·Curing accelerator: Mixing amount = 0.42 parts by mass

2-Phenyl-4,5-dihydroxymethyl imidazole (manufactured by SHIKOKU CHEMICALS CORPORATION, product name “Curezol 2 PHZ”), equivalent to the above ingredient (B3).

·Colorant: Mixing amount = 0.20 parts by mass

Carbon black (manufactured by Mitsubishi Chemical Corporation, product name “#MA650”, average particle size = 28 nm), equivalent to the above component (C).

·Silane coupling agent: Mixing amount = 0.09 parts by mass

3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM403”), molecular weight = 236.64, equivalent to the above component (D).

·Weapon filler: Mixing amount = 55.5 parts by mass

Silica filler (manufactured by Admatechs, product name “SC2050MA”, average particle size = 0.5 μm), equivalent to the above component (E).

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

＜Adhesive Resin＞

·Acrylic copolymer (i): An acrylic copolymer having an Mw of only 60, having a constituent unit derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2 EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio).

·Acrylic copolymer (ii): An acrylic copolymer having an Mw of 600,000, having a constituent unit derived from a raw material monomer consisting of n-butyl acrylate (BA)/methyl methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid = 86.0/8.0/5.0/1.0 (mass ratio).

＜Additives＞

·Isocyanate crosslinking agent (i): TOSOH CORPORATION, product name “Coronate L”, solid content concentration: 75 mass%.

＜Thermal Expansion Particles＞

·Thermal expandable particles (i): KUREHA CORPORATION, product name "S2640", expansion start temperature (t) = 208℃, average particle diameter (D ₅₀ ) = 24㎛, 90% particle diameter (D ₉₀ ) = 49㎛.

＜Park Li-jae＞

·Heavy-duty release film: Manufactured by LINTEC Corporation, product name "SP-PET382150", a release agent layer formed with a silicone-based release agent is installed on one side of a polyethylene terephthalate (PET) film, thickness: 38 μm.

·Light release film: Manufactured by LINTEC Corporation, product name "SP－PET381031", a release agent layer formed with a silicone-based release agent is installed on one side of the PET film, thickness: 38㎛.

Example 1

In the adhesive laminate (2b) shown in Fig. 2(b), an adhesive laminate having a configuration in which a release agent is further laminated on the second adhesive layer (X2) of the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film was produced in the following order.

[1] Production of adhesive sheet (I)

(1-1) Formation of the first adhesive layer (X1)

To 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, 5.0 parts by mass (solid content ratio) of the isocyanate crosslinking agent (i) was mixed, diluted with toluene, and stirred uniformly to prepare an adhesive composition having a solid content concentration (effective ingredient concentration) of 25% by mass.

Then, the adhesive composition was applied to the surface of the release agent layer of the above-mentioned heavy-duty film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a first adhesive layer (X1) which is a non-thermally expandable adhesive layer having a thickness of 5 μm.

Additionally, the storage shear modulus G'(23) of the first adhesive layer (X1) at 23°C was 2.5×10 ⁵ Pa.

Additionally, the adhesive strength of the first adhesive layer (X1) measured based on the above method was 0.3 N/25 mm.

(1-2) Formation of the second adhesive layer (X2)

To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 0.8 parts by mass (solid content ratio) of the isocyanate crosslinking agent (i) was mixed, diluted with toluene, and stirred uniformly to prepare an adhesive composition having a solid content concentration (effective ingredient concentration) of 25% by mass.

Then, the adhesive composition was applied to the surface of the release layer of the light-release film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a second adhesive layer (X2) having a thickness of 10 μm.

Additionally, the storage shear modulus G'(23) of the second adhesive layer (X2) at 23°C was 9.0×10 ⁴ Pa.

Additionally, the adhesive strength of the second adhesive layer (X2) measured based on the above method was 1.0 N/25 mm.

(1-3) Production of the device (Y)

In 100 parts by mass of the acrylic urethane resin obtained in Manufacturing Example 2, 6.3 parts by mass (solid content ratio) of the isocyanate crosslinking agent (i), 1.4 parts by mass (solid content ratio) of dioctyl tin bis(2-ethylhexanoate) as a catalyst, and the heat-expandable particles (i) were mixed, diluted with toluene, and stirred uniformly to prepare a resin composition having a solid content concentration (effective ingredient concentration) of 30% by mass.

In addition, the content of the heat-expandable particles (i) was 20 mass% with respect to the total amount (100 mass%) of the effective ingredient in the obtained resin composition.

Then, the resin composition was applied onto the surface of a 50 ㎛ thick polyethylene terephthalate (PET) film (manufactured by TOYOBO CO., LTD., product name “Cosmo Shine A4100”, probe tack value: 0 mN/5 mmφ), which is a non-thermal expansion substrate, to form a coating film, and the coating film was dried at 100° C. for 120 seconds to form an expandable substrate layer (Y1) with a thickness of 50 ㎛.

Here, the PET film, which is the non-expandable substrate, corresponds to the non-expandable substrate layer (Y2).

In this manner, a substrate (Y) comprising an expandable substrate layer (Y1) having a thickness of 50 μm and a non-expandable substrate layer (Y2) having a thickness of 50 μm was manufactured.

In addition, as a sample for measuring the physical properties of the intumescent substrate layer (Y1), the resin composition was applied to the surface of the release agent layer of the light-release film to form a coating film, and the coating film was dried at 100° C. for 120 seconds to similarly form an intumescent substrate layer (Y1) having a thickness of 50 μm.

And, based on the measurement method described above, the storage elastic modulus and probe tack value of the intumescent substrate layer (Y1) at each temperature were measured. The measurement results were as follows.

·Storage elastic modulus E＇(23)=2.0× ^108Pa at 23℃

·Storage elastic modulus at 100℃ E＇(100)=3.0× ¹⁰⁶ Pa

·Storage elastic modulus at 208℃ E＇(208)=5.0×10 ⁵ Pa

·Probe tack value = 0 mN/5mmφ

(1-4) Lamination of each layer

The non-expandable substrate layer (Y2) of the substrate (Y) manufactured in the above (1-3) and the second adhesive layer (X2) formed in the above (1-2) were bonded together, and at the same time, the expandable substrate layer (Y1) and the first adhesive layer (X1) formed in the above (1-1) were bonded together.

And, an adhesive sheet (I) was manufactured by laminating in this order a light release film/second adhesive layer (X2)/non-expandable substrate layer (Y2)/expandable substrate layer (Y1)/first adhesive layer (X1)/heavy release film.

[2] Production of sheet (II) for forming a cured resin film

A solution of the curable composition prepared in Manufacturing Example 3 was applied onto the peeling-treated surface of the above-mentioned light-release film to form a coating film, and the coating film was dried at 120°C for 2 minutes to form a thermosetting resin layer (Z) having a thickness of 25 μm, thereby producing a sheet (II) for forming a cured resin film comprising a thermosetting resin layer (Z) and a light-release film.

Additionally, the adhesive strength of the formed thermosetting resin layer (Z) was 0.5 N/25 mm.

In addition, the storage elastic modulus E' of the cured resin film after heat curing of the thermosetting resin layer (Z) was 6.5×10 ⁹ Pa.

[3] Production of adhesive laminate

The release film of the adhesive sheet (I) manufactured in the above [1] was removed, and the first adhesive layer (X1) that was exposed and the surface of the thermosetting resin layer (Z) that was exposed of the sheet (II) for forming a cured resin film were bonded together to obtain an adhesive laminate.

For the above-mentioned adhesive laminate, before and after the heat treatment, which is an expansion treatment, the peeling force (F ₀ ) and (F ₁ ) at the interface P between the first adhesive layer (X1) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film were measured based on the following method.

As a result, the peeling force (F ₀ ) when separating from the interface P before heat treatment = 200 mN/25 mm, and the peeling force (F ₁ ) when separating from the interface P after heat treatment = 0 mN/25 mm, so the ratio of the peeling force (F ₁ ) and the peeling force (F ₀ ) [(F ₁ )/(F ₀ )] was 0.

＜Measurement of peeling force (F ₀ )＞

After the manufactured adhesive laminate was left to stand for 24 hours in an environment of 23°C and 50% RH (relative humidity), the release film on the adhesive sheet (I) side of the adhesive laminate was removed, and the exposed second adhesive layer (X2) was attached to a stainless steel plate (SUS304, polished 360 times).

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 testing machine (product name “Tensilon UTM-4-100” manufactured by ORIENTEC Co., LTD.).

In addition, the sheet (II) for forming a cured resin film of the adhesive laminate was fixed to the upper chuck of a universal tensile tester so as to peel off at the interface P between the first adhesive layer (X1) of the adhesive sheet (I) of the adhesive laminate and the sheet (II) for forming a cured resin film.

And, under the above environment, based on JIS Z0237:2000, in accordance with the 180° peeling method, when peeling was performed at the interface P at a tensile speed of 300 mm/min, the measured peeling force was referred to as the “peel force (F ₀ ).”

＜Measurement of peeling force (F ₁ )＞

The release film on the adhesive sheet (I) side of the manufactured adhesive laminate was removed, and the exposed second adhesive layer (X2) was attached to a stainless steel plate (SUS304, polished 360 times).

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 layer (Y1) of the adhesive laminate.

Next, similarly to the measurement of the peeling force (F ₀ ) described above, the peeling force measured when peeling occurred at the interface P between the first adhesive layer (X1) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film under the above conditions was referred to as the “peeling force (F ₁ ).”

In addition, in the measurement of the peeling force (F ₁ ), when attempting to fix the sheet (II) for forming a cured resin film of the adhesive laminate to the upper chuck of the universal tensile tester, if the sheet (II) for forming a cured resin film completely separates at the interface P and fixing is not possible, the measurement is terminated, and the peeling force (F ₁ ) at this time is defined as “0 mN/25 mm”.

Example 2

A cured encapsulation body having a cured resin film was manufactured in the following order.

(1) The ingenuity of semiconductor chips

The release film on the adhesive sheet (I) side of the adhesive laminate produced in Example 1 was removed, and the adhesive surface of the second adhesive layer (X2) of the exposed adhesive sheet (I) was attached to a support (glass).

Then, the light-release film on the side of the sheet (II) for forming the cured resin film was also removed, and nine semiconductor chips (each chip size was 6.4 mm × 6.4 mm, and the chip thickness was 200 ㎛ (#2000)) were placed on the surface of the exposed thermosetting resin layer (Z) at the necessary intervals so that the back surface of each semiconductor chip, opposite to the circuit surface, was in contact with the surface.

(2) Formation of hardened capsules

The surfaces of the thermosetting resin layer (Z) of the nine semiconductor chips and at least the peripheral portions of the semiconductor chips were covered with a thermosetting encapsulating resin film, which is a sealing material, and a vacuum heating and pressure laminator ("7024 HP5" manufactured by ROHM and HAAS) was used to heat-cur the encapsulating resin film, thereby producing a cured encapsulating body.

Also, the bagging conditions are as follows.

·Preheating temperature: 100℃ for both table and diaphragm

·Vacuum: 60 seconds

·Dynamic press mode: 30 seconds

·Static press mode: 10 seconds

·Bag temperature: 180℃×60 minutes

In addition, along with the thermal curing of the bag resin film, the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film was also cured under the above-mentioned environment to form a cured resin film.

(3) Separation at interface P

After the above (2), a heat treatment was performed at 240°C for 3 minutes, which is higher than the expansion initiation temperature (208°C) of the heat-expandable particles. Then, the first adhesive layer (X1) of the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film were easily and collectively separated at the interface P of the cured resin film formed by thermal curing.

After separation at interface P, a cured encapsulated body having a cured resin film was obtained.

In addition, the cured encapsulated body having the obtained cured resin film was cooled to room temperature (25°C), but no warping was observed.

1a, 1b, 2a, 2b, 3 adhesive laminates
(I) Adhesive sheet
(X) Adhesive layer
(X1) First adhesive layer
(X2) Second adhesive layer
(Y) Description
(Y1) Thermal expansion substrate layer
(Y2) Non-thermal expansion substrate layer
(II) Sheet for forming a cured resin film
(Z) Thermosetting resin layer
(Z') Cured resin film
Interface between P adhesive sheet (I) and sheet for forming cured resin film (II)
50 support
60 bags of objects
70 bag materials
80 hardened bag
Curing bag having 100 curing resin film

Claims (15)

An expandable adhesive sheet (I) having a substrate (Y) and an adhesive layer (X), wherein one of the layers contains expandable particles, and
A sheet (II) for forming a cured resin film having a thermosetting resin layer (Z) is provided.
An adhesive laminate formed by directly laminating an adhesive sheet (I) and a thermosetting resin layer (Z) of a sheet (II) for forming a cured resin film,
The substrate (Y) has an expandable substrate layer (Y1) containing expandable particles,
An adhesive laminate, which is separated at the interface P between the adhesive sheet (I) and the sheet (II) for forming a cured resin film by a treatment for expanding the above-mentioned expandable particles. In the first paragraph,
An adhesive laminate wherein the above expandable particles are heat-expandable particles. In paragraph 1 or 2,
An adhesive laminate, wherein the thermosetting resin layer (Z) is a layer formed of a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B). In paragraph 1 or 2,
The adhesive layer (X) of the adhesive sheet (I) is composed of a first adhesive layer (X1) and a second adhesive layer (X2).
The substrate (Y) is sandwiched between the first adhesive layer (X1) and the second adhesive layer (X2),
An adhesive laminate having an adhesive surface of a first adhesive layer (X1) that is directly laminated with a thermosetting resin layer (Z). In paragraph 1 or 2,
The adhesive layer (X) is an adhesive laminate that is a non-intumescent adhesive layer. In paragraph 1 or 2,
The substrate (Y) is an adhesive laminate having an intumescent substrate layer (Y1) and a non-intumescent substrate layer (Y2). In Article 6,
A first adhesive layer (X1) is laminated on the surface of the inflatable substrate layer (Y1),
An adhesive laminate having a configuration in which a second adhesive layer (X2) is laminated on the surface of a non-intumescent substrate layer (Y2). In Article 7,
An adhesive laminate, wherein the first adhesive layer (X1) and the second adhesive layer (X2) are non-intumescent adhesive layers. In paragraph 1 or 2,
The sheet (II) for forming a cured resin film is an adhesive laminate composed only of a thermosetting resin layer (Z). In paragraph 1 or 2,
Place the bagging object on the surface of the sheet (II) for forming a cured resin film,
An adhesive laminate used to form a cured encapsulation body including the encapsulation object by covering the surface of the encapsulation object and at least the peripheral portion of the encapsulation object with a encapsulation material and thermally curing the encapsulation material. In Article 10,
When the above-mentioned encapsulating material is heat-cured, the thermosetting resin layer (Z) can also be heat-cured to form a cured resin film.
An adhesive laminate used to obtain a cured encapsulated body having a cured resin film by separating the above-mentioned expandable particles from the interface P through an expanding treatment. In paragraph 1 or 2,
An adhesive laminate, wherein the expandable base layer (Y1) is formed from a resin composition (y) comprising at least one selected from an acrylic urethane resin and an olefin resin, and the expandable particles. A method of using the adhesive laminate described in claim 1 or claim 2,
Place the bagging object on the surface of the sheet (II) for forming a cured resin film,
A method for using an adhesive laminate, comprising covering the surface of the above-mentioned bagging object and at least the periphery of the above-mentioned bagging object and a sheet (II) for forming a cured resin film with a bagging material, and thermally curing the bagging material to form a cured bagging body including the above-mentioned bagging object. In Article 13,
When the above encapsulating material is cured, the thermosetting resin layer (Z) is also cured to form a cured resin film.
A method for using an adhesive laminate, wherein the above expandable particles are separated from the interface P by an expanding treatment, thereby obtaining a cured encapsulated body having a cured resin film. A method for manufacturing a cured encapsulating body having a cured resin film by using the adhesive laminate described in claim 1 or claim 2, the method comprising the following steps (i) to (iii).
·Process (i): A process of attaching the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate and a support to place an object to be sealed on part of the surface of the sheet (II) for forming a cured resin film.
·Process (ii): A process of covering the surface of the sheet (II) for forming a cured resin film on at least the peripheral portion of the above-mentioned sealing object and the above-mentioned sealing object with a sealing material, thermally curing the sealing material to form a cured sealing body including the above-mentioned sealing object, and simultaneously thermally curing the thermosetting resin layer (Z) to form a cured resin film.
·Process (iii): A process for obtaining a cured encapsulated body having a cured resin film by separating the expandable particles from the interface P through a treatment for expanding the expandable particles.