CN111902508A - Adhesive laminate, method for using adhesive laminate, and method for producing cured sealing body with cured resin film - Google Patents

Abstract

The present invention relates to an adhesive laminate comprising an expandable pressure-sensitive adhesive sheet (I) having a base material (Y) and a pressure-sensitive adhesive layer (X) and including expandable particles in any layer, and a thermosetting adhesive sheet The cured resin film-forming sheet (II) of the resin layer (Z), and the adhesive sheet (I) and the thermosetting resin layer (Z) of the cured resin film-forming sheet (II) are directly laminated together, wherein the adhesive The flexible laminate is separated at the interface P between the pressure-sensitive adhesive sheet (I) and the sheet (II) for forming a cured resin film by the process of expanding the expandable particles.

Description

Adhesive laminate, method of using adhesive laminate, and cured resin film A method of manufacturing a cured seal

technical field

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

Background technique

The pressure-sensitive adhesive sheet is used not only for semi-permanently fixing members, but also for temporarily fixing target members during processing or inspection of building materials, interior materials, electronic components, and the like.

For such a PSA sheet for temporary fixing, both the adhesiveness during use and the releasability after use are required.

For example, Patent Document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component, which is provided with a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres on at least one surface of a base material. .

In this heat-peelable pressure-sensitive adhesive sheet, the maximum particle diameter of the heat-expandable microspheres was adjusted relative to the thickness of the heat-expandable pressure-sensitive adhesive layer, and the centerline average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating was adjusted to 0.4 μm the following.

Patent Document 1 describes the following points: Since the heat-peelable pressure-sensitive adhesive sheet can sufficiently secure the adhesion area with the adherend when the electronic component is cut, it can exert an adhesive force that can prevent poor adhesion such as chip flyout. On the other hand, after use, if the heat-expandable microspheres are expanded by heating, the contact area with the adherend can be reduced, and peeling can be easily achieved.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent No. 3594853

SUMMARY OF THE INVENTION

The problem to be solved by the invention

In the process of processing using the pressure-sensitive adhesive sheet described in Patent Document 1, an object to be processed (hereinafter, also referred to as "object to be processed") is temporarily fixed using the pressure-sensitive adhesive sheet, and the object to be processed is subjected to After processing, the object to be processed is separated from the pressure-sensitive adhesive sheet.

On the other hand, as the above-mentioned processing, a sealing process may be performed in which an object to be processed such as a semiconductor chip is covered with a sealing material containing a curable resin, and the sealing material is cured to form a cured sealing body.

Among them, when the above-mentioned sealing process is performed using the PSA sheet described in Patent Document 1, when the PSA sheet is separated from the cured sealing body by heating after forming the cured sealing body, there is curing after separation. The sealing body tends to warp due to thermal shrinkage.

For example, when the cured sealing body is warped and the surface is uneven, for example, when the cured sealing body is ground in the subsequent process, the disadvantages such as cracking are likely to occur, or when the cured sealing body is conveyed by the equipment, the use of When the robot arm is handed over to cure the sealing body, problems are likely to occur.

In addition, a resin film may be further provided on one surface of the cured sealing body to form a cured sealing body with a resin film.

When manufacturing such a cured sealing body with a resin film, it is usually necessary to form a resin film by attaching a separately prepared sheet for forming a resin film to one surface of the cured sealing body to be formed and curing the sheet for forming a resin film. process.

In addition, since the cured sealing body is prone to warp at the time of manufacture as described above, the workability at the time of sticking the sheet for resin film formation is lowered due to the warpage of the cured sealing body, and curing The adhesiveness between the obtained resin film and the cured sealing body reduces these problems.

In addition, the obtained cured sealing body with a resin film may further increase in warpage, and thus various disadvantages may be caused in subsequent steps.

An object of the present invention is to provide an adhesive laminate which can be sealed by fixing an object to be sealed to a support and can be easily detached from the support at one time with a small force after the sealing, and, The cured sealing body with a cured resin film having a flat surface with suppressed warpage can be produced by improving productivity.

way of solving the problem

The inventors of the present invention have found that the above-mentioned problems can be solved by an adhesive laminate having a structure including an expansible adhesive sheet (I) and a sheet for forming a cured resin film (II), The expandable pressure-sensitive adhesive sheet (I) has a base material and a pressure-sensitive adhesive layer, and includes a layer containing expandable particles in any layer, and the cured resin film-forming sheet (II) includes a thermosetting resin layer (Z), And the thermosetting resin layer (Z) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film are directly laminated together.

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

[1] An adhesive laminate comprising:

An expandable pressure-sensitive adhesive sheet (I) having a base material (Y) and a pressure-sensitive adhesive layer (X) and containing expandable particles in any layer, and

A sheet (II) for forming a cured resin film having a thermosetting resin layer (Z),

And the thermosetting resin layer (Z) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film are directly laminated together,

However, this adhesive laminated body is isolate|separated at the interface P of the adhesive sheet (I) and the sheet (II) for cured resin film formation by the process which expands the said expandable particle.

[2] The adhesive laminate according to the above [1], wherein the expandable particles are thermally expandable particles.

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

[4] The adhesive laminate according to any one of the above [1] to [3], which has the following configuration:

The pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet (I) includes a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), and the base material (Y) is covered by the first pressure-sensitive adhesive layer (X2). X1) and the second pressure-sensitive adhesive layer (X2) are sandwiched, and the bonding surface of the first pressure-sensitive adhesive layer (X1) and the thermosetting resin layer (Z) are directly laminated.

[5] The adhesive laminate according to any one of the above [1] to [4], wherein the base material (Y) has an expandable base material layer (Y1) containing expandable particles.

[6] The pressure-sensitive adhesive laminate according to the above [5], wherein the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer.

[7] The adhesive laminate according to the above [5], wherein the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2).

[8] The adhesive laminate according to the above [7], which has the following structure:

The first pressure-sensitive adhesive layer (X1) is laminated on the surface of the intumescent base material layer (Y1), and the second pressure-sensitive adhesive layer (X2) is laminated on the surface of the non-expandable base material layer (Y2).

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

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

[11] The adhesive laminate according to any one of the above [1] to [10], which is used for:

The object to be sealed is placed on the surface of the sheet (II) for forming a cured resin film,

The above-mentioned object to be sealed and the surface of the sheet (II) for forming a cured resin film in at least a peripheral portion of the object to be sealed are covered with a sealing material, and the sealing material is thermally cured to form a cured material including the above-mentioned object to be sealed sealing body.

[12] The adhesive laminate according to the above [11], wherein

When the above-mentioned sealing material is thermally cured, the thermosetting resin layer (Z) is also thermally cured, whereby a cured resin film can be formed,

This adhesive laminate is used to obtain a cured sealing body with a cured resin film by separating at the interface P by the process of expanding the above-mentioned expandable particles.

[13] A method of using an adhesive laminate, which is the method of using the adhesive laminate according to any one of the above [1] to [12], the method comprising:

The object to be sealed is placed on the surface of the sheet (II) for forming a cured resin film, the object to be sealed and at least the surface of the sheet (II) for forming a cured resin film of the peripheral portion of the object to be sealed are covered with a sealing material , the sealing material is thermally cured to form a cured sealing body containing the above-mentioned sealing object.

[14] The method of using the adhesive laminate according to the above [13], wherein

When curing the sealing material, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, and at the same time, the adhesive laminate is separated at the interface P by the treatment of expanding the expandable particles. Thus, a cured sealing body with a cured resin film was obtained.

[15] A method for producing a cured seal body with a cured resin film, comprising using the adhesive laminate according to any one of the above [1] to [12] to manufacture a cured seal body with a cured resin film The method comprising the following steps (i) to (iii):

Step (i): The adhesive surface of the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet (I) included in the pressure-sensitive adhesive laminate is affixed to the support, and the adhesive layer (II) of the sheet (II) for forming a cured resin film is attached to the adhesive surface. A step of placing an object to be sealed on a part of the surface.

Step (ii): Covering the object to be sealed and the surface of the sheet (II) for forming a cured resin film in at least a peripheral portion of the object to be sealed with a sealing material, and thermally curing the sealing material to form a composition comprising the A step of forming a cured resin film by thermally curing the thermosetting resin layer (Z) at the same time as the cured sealing body of the sealing object.

- Process (iii): the process of separating the said adhesive laminated body at the interface P by the process of swelling the said expandable particle, and the process of hardening the sealing body with a cured resin film.

effect of invention

The adhesive laminate of the present invention can be easily separated from the support at one time with a small force after the sealing process can be performed by fixing the object to be sealed to the support body.

Moreover, by using this adhesive laminated body, productivity can be improved, and the cured sealing body with a cured resin film which has a flat surface with suppressed curvature can be manufactured.

Description of drawings

[ Fig. 1] Fig. 1 is a schematic cross-sectional view of the adhesive laminate showing the configuration of the adhesive laminate according to the first embodiment of the present invention.

[ Fig. 2] Fig. 2 is a schematic cross-sectional view of the adhesive laminate showing the configuration of the adhesive laminate according to the second embodiment of the present invention.

[ Fig. 3] Fig. 3 is a schematic cross-sectional view of the adhesive laminate showing the configuration of the adhesive laminate according to the third embodiment of the present invention.

[ Fig. 4] Fig. 4 is a schematic cross-sectional view showing a step of producing a cured sealing body with a cured resin film using the adhesive laminate 1a shown in Fig. 1(a) .

Symbol Description

1a, 1b, 2a, 2b, 3: Adhesive laminate

(I) Adhesive sheet

(X) Adhesive layer

(X1) 1st pressure-sensitive adhesive layer

(X2) Second adhesive layer

(Y) Substrate

(Y1) Thermally expandable base material layer

(Y2) Non-thermally expandable base material layer

(II) Sheet for Cured Resin Film Formation

(Z) Thermosetting resin layer

(Z') Cured resin film

Interface between P pressure-sensitive adhesive sheet (I) and cured resin film-forming sheet (II)

50 Support

60 Sealed objects

80 Sealing material

100 Cured Seal with Cured Resin Film

Detailed ways

In the present specification, whether or not the target layer is a "non-expandable layer" can be determined as follows: after performing the treatment for swelling for 3 minutes, the volume change rate before and after the treatment calculated by the following formula is less than 5 volumes In the case of %, the layer was judged to be a "non-expandable layer".

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

In addition, as "treatment for expanding", for example, in the case of a layer containing heat-expandable particles, the heat-treatment is performed at the expansion start temperature (t) of the heat-expandable particles for 3 minutes, that is, Can.

In the present specification, the "active ingredient" refers to a component other than the dilution solvent among the components contained in the target composition.

In this specification, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene, and specifically is a value measured by the method described in Examples.

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

In this specification, regarding the preferable numerical range (for example, the range of content etc.), the lower limit value and upper limit value described in each segment can be combined independently. For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", "preferable lower limit value (10)" and "more preferred upper limit value (60)" can also be obtained by combining "10 to 60".

[Properties of Adhesive Laminates]

The pressure-sensitive adhesive laminate of the present invention has a structure including an expandable pressure-sensitive adhesive sheet (I) having a base material (Y) and a pressure-sensitive adhesive layer (X) and including expandable particles in any layer, and a thermosetting The cured resin film forming sheet (II) of the resin layer (Z), and the adhesive sheet (I) and the thermosetting resin layer (Z) of the cured resin film forming sheet (II) are directly laminated together.

The pressure-sensitive adhesive laminate of the present invention can be adhered to the adhesive sheet (I) by making any layer of the pressure-sensitive adhesive sheet (I) a layer containing expandable particles, and by a treatment for expanding the expandable particles (hereinafter also referred to as "expansion treatment"). The interface P of the laminated sheet (I) and the sheet for cured resin film formation (II) is separated.

That is, in the pressure-sensitive adhesive laminate of the present invention, the expandable particles are expanded by the expansion treatment, so that irregularities are generated on the surface of the layer containing the expandable particles, and the pressure-sensitive adhesive sheet (I) and the cured resin film are formed The contact area with sheet (II) is reduced. As a result, the interface P between the adhesive sheet (I) and the sheet for forming a cured resin film (II) can be easily separated at one time with a small force.

In addition, it can select according to the kind of the swellable particle used as a process to swell the swellable particle at the time of separation of the interface P.

For example, when heat-expandable particles are used, it is appropriate to perform heat treatment at a temperature equal to or higher than the expansion start temperature (t) of the heat-expandable particles.

In addition, the adhesive laminate of the present invention includes a sheet (II) for forming a cured resin film having a thermosetting resin layer (Z), and is formed so that one surface of the thermosetting resin layer (Z) is directly connected to the adhesive sheet (I). Composition layered together.

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

The adhesive laminate of the present invention is preferably used in a case where a sealing object is placed on the surface of the sheet (II) for forming a cured resin film, and the sealing object and at least a peripheral portion of the sealing object are covered with a sealing material. The said surface of the sheet (II) for resin film formation is cured, and this sealing material is thermosetted, and the cured sealing body containing the said sealing object is formed.

In addition, the adhesive laminate of the present invention is more preferably used for forming a cured resin film by thermally curing the thermosetting resin layer (Z) when the above-mentioned sealing material is thermally cured. The particles are swelled to separate at the interface P, and a cured sealing body with a cured resin film is obtained.

For example, after placing the object to be sealed on the adhesive surface of the pressure-sensitive adhesive sheet described in Patent Document 1, it is conceivable that the object to be sealed and the adhesive surface of the peripheral portion thereof are covered with a sealing material, and the sealing material is heated. cured to produce a cured seal.

When the sealing material is thermally cured, the stress of shrinkage of the sealing material acts, but since the pressure-sensitive adhesive sheet is fixed to the support, the stress of the sealing material is suppressed.

However, it is difficult to suppress the stress that causes shrinkage of the cured sealing body separated from the support body and the pressure-sensitive adhesive sheet. In the cured sealing body after separation, the amount of the sealing material is different between the surface side on which the object to be sealed is present and the surface side opposite thereto, and therefore, a difference in shrinkage stress is likely to occur. This difference in shrinkage stress causes warpage of the cured sealing body.

In addition, from the viewpoint of productivity, in general, the cured sealing body after heating is separated from the support body and the pressure-sensitive adhesive sheet in a state with a certain degree of heat. Therefore, after separation, the solidification of the sealing material progresses, and at the same time, shrinkage accompanying natural cooling occurs, and therefore, the cured sealing body is in a state where warpage is more likely to occur.

On the other hand, the adhesive laminated body of this invention can suppress the curvature of a cured sealing body by providing the sheet (II) for cured resin film formation which has a thermosetting resin layer (Z) for the following reasons.

That is, when the object to be sealed is placed on the surface of the sheet (II) for forming a cured resin film, and the sealing material is thermally cured after being covered with a sealing material, the thermosetting resin layer (Z) is also thermally 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 object exists in a small amount of the sealing material and the shrinkage stress due to curing of the sealing material is considered to be small, the thermosetting resin layer is formed by the thermosetting resin layer (Z). Shrinkage stress due to thermal curing of (Z) acts.

As a result, it is considered that the difference in shrinkage stress between the two surfaces of the cured seal body can be reduced, and a cured seal body in which warpage is effectively suppressed can be obtained.

In addition, the thermosetting resin layer (Z) which contributes to suppressing the warpage of the cured sealing body can be formed as a cured resin film by thermal curing. Furthermore, it is considered that by performing the expansion treatment described above to separate at the interface P, a cured sealing body with a cured resin film having a flat surface with suppressed warpage can be produced without going through a separate step for forming the cured resin film.

[Configuration of Adhesive Laminate]

1-3 is a cross-sectional schematic diagram of the adhesive laminated body which shows the structure of the adhesive laminated body of the 1st - 3rd embodiment of this invention. Hereinafter, the structure of the adhesive laminated body shown in FIGS. 1-3 which is one Embodiment of this invention is demonstrated.

In addition, in the adhesive laminates of the following first to third embodiments of the present invention, the adhesive layer (X) (or the second adhesive layer) to be attached to the support may be formed. The adhesive surface of the mixture layer (X2)) and the surface on the opposite side of the adhesive sheet (I) side of the sheet (II) for forming a cured resin film are further laminated with a release material.

<The adhesive laminate of the first embodiment>

As an adhesive laminated body which concerns on 1st Embodiment of this invention, the adhesive laminated body 1a, 1b shown in FIG. 1 is mentioned.

The adhesive laminates 1a and 1b have the following configurations: an adhesive sheet (I) having a base material (Y) and an adhesive layer (X), and a thermosetting resin layer (Z) for forming a cured resin film sheet (II), and the base material (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 together.

On the other hand, the pressure-sensitive adhesive sheet (I) included in the pressure-sensitive adhesive laminate of the present invention contains expandable particles in any layer.

As shown in FIG. 1, the adhesive laminated body of the 1st Embodiment of this invention has a base material (Y) which has an expandable base material layer (Y1) containing an expandable particle.

The base material (Y) having the intumescent base material layer (Y1) may be a single layer composed of only the intumescent base material layer (Y1), as in the adhesive laminate 1a shown in Fig. 1(a) . The base material of the structure may be a base of a multilayer structure having an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) as in the adhesive laminate 1b shown in FIG. 1(b) . material.

In the pressure-sensitive adhesive laminate 1a shown in FIG. 1(a) , the expandable particles contained in the expandable base material layer (Y1) are expanded by the expansion treatment, and are generated on the surface of the expandable base material layer (Y1). The unevenness reduces the contact area with the thermosetting resin layer (Z).

On the other hand, by sticking in such a manner that the adhesive surface of the adhesive layer (X) and the support are sufficiently brought into close contact, although the surface on the adhesive layer (X) side of the intumescent base layer (Y1) A force that generates unevenness is generated, and a force that is easily repelled from the pressure-sensitive adhesive layer is also generated. Therefore, unevenness is less likely to be formed on the surface of the expansible base material layer (Y1) on the adhesive layer (X) side.

As a result, in the adhesive laminate 1a, the interface P between the base material (Y) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film can be easily performed at one time with a small force. separation.

In addition, by forming the adhesive layer (X) which the adhesive laminated body 1a has with the adhesive composition which can improve the adhesive force with respect to the support body, it can also be designed so that the interface P Separation can be carried out more easily.

In addition, from the viewpoint of suppressing the transfer of the stress caused by the intumescent particles to the pressure-sensitive adhesive layer (X) side, it is preferable to make the base material ( Y) has an intumescent base material layer (Y1) and a non-expandable base material layer (Y2).

Since the stress caused by the expansion of the expandable particles of the expandable base material layer (Y1) can be suppressed by the non-expandable base material layer (Y2), it is not substantially transmitted to the pressure-sensitive adhesive layer (X).

Therefore, the adhesiveness with the support body of the pressure-sensitive adhesive layer (X) is not substantially changed before and after the expansion treatment, and the adhesiveness with the support body can be maintained favorably.

In addition, it is preferable that the thermosetting resin layer (Z) of the intumescent base material layer (Y1) and the sheet (II) for cured resin film formation be directly like the adhesive laminated body 1b shown in FIG.1(b) A structure in which the adhesive layer (X) is laminated together on the surface of the non-expandable base material layer (Y2).

<The adhesive laminate of the second embodiment>

As an adhesive laminated body of 2nd Embodiment of this invention, the adhesive laminated bodies 2a and 2b shown in FIG. 2 are mentioned.

The pressure-sensitive adhesive laminates 2a and 2b have a structure in which the pressure-sensitive adhesive layer (X) included in the pressure-sensitive adhesive sheet (I) includes a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), The base material (Y) is sandwiched by the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), and the bonding surface of the first pressure-sensitive adhesive layer (X1) and the thermosetting resin layer (Z) directly stacked together.

In addition, in the adhesive laminated body of 2nd Embodiment of this invention, the adhesive surface of a 2nd adhesive layer (X2) is stuck to a support body.

Also in the adhesive laminate of the second embodiment of the present invention, the base material (Y) preferably has an expandable base material layer (Y1) containing expandable particles.

As the base material (Y) having the intumescent base material layer (Y1), a single layer composed of only the intumescent base material layer (Y1) may be used as the adhesive laminate 2a shown in Fig. 2(a) . The base material of the structure may be the base of a multilayer structure having an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) as in the adhesive laminate 2b shown in FIG. 2(b) . material.

Among them, as described above, it is preferable that the base material (Y) has swelling, from the viewpoint of obtaining an adhesive laminate which can keep the adhesion between the second pressure-sensitive adhesive layer (X2) and the support well before and after the swelling treatment. The flexible base material layer (Y1) and the non-expandable base material layer (Y2).

In addition, in the adhesive laminated body of 2nd Embodiment of this invention, when using the base material (Y) which has an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) , preferably, as shown in FIG. 2(b), the first adhesive layer (X1) is laminated on the surface of the intumescent substrate layer (Y1), and the surface of the non-intumescent substrate layer (Y2) A structure in which a second pressure-sensitive adhesive layer (X2) is laminated thereon.

In the adhesive laminate according to the second embodiment of the present invention, the expandable particles in the expandable base material layer (Y1) constituting the base material (Y) are expanded by the expansion treatment, so that the expandable base material layer is swelled. The surface of (Y1) has irregularities.

Furthermore, the first pressure-sensitive adhesive layer (X1) is also lifted up due to the unevenness generated on the surface of the intumescent base material layer (Y1), and the first pressure-sensitive adhesive layer (X1) is also formed on the adhesion surface of the first pressure-sensitive adhesive layer (X1). Because of the unevenness, the contact area between the first pressure-sensitive adhesive layer (X1) and the thermosetting resin layer (Z) is reduced.

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

In addition, in the adhesive laminate of the second embodiment of the present invention, from the viewpoint of obtaining an adhesive laminate which can be easily separated at one time with a smaller force at the interface P, it is preferable to It is a structure in which the expandable base material layer (Y1) of the base material (Y) and the first pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) are directly laminated.

<Adhesive laminate of the third embodiment>

As an adhesive laminated body of 3rd Embodiment of this invention, the adhesive laminated body 3 shown in FIG. 3 is mentioned.

The adhesive laminate 3 shown in FIG. 3 has a structure including a pressure-sensitive adhesive sheet (I), and the pressure-sensitive adhesive sheet (I) has, on one surface side of the base material (Y), a The first pressure-sensitive adhesive layer (X1) of the intumescent pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer (X2) as a non-expandable pressure-sensitive adhesive layer on the other surface side of the base material (Y), and the The first pressure-sensitive adhesive layer (X1) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are directly laminated.

In the adhesive laminated body 3, the adhesive surface of the 2nd adhesive layer (X2) is stuck to a support body.

In addition, it is preferable that the base material (Y) which the adhesive laminated body which concerns on 3rd Embodiment of this invention has consists of a non-expandable base material layer.

In the pressure-sensitive adhesive laminate of the third embodiment of the present invention, the expandable particles in the first pressure-sensitive adhesive layer (X1) serving as the expandable pressure-sensitive adhesive layer are expanded by the expansion treatment, and the first pressure-sensitive adhesive layer is formed in the first pressure-sensitive adhesive layer. The surface of the agent layer (X1) has irregularities, and the contact area between the first adhesive layer (X1) and the thermosetting resin layer (Z) decreases.

On the other hand, since the base material (Y) is laminated on the surface of the first pressure-sensitive adhesive layer (X1) on the side of the base material (Y), unevenness is less likely to occur.

Therefore, by the expansion treatment, unevenness is easily formed on the surface on the side of the thermosetting resin layer (Z) of the first pressure-sensitive adhesive layer (X1), and as a result, the first pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) The interface P with the sheet (II) for forming a cured resin film can be easily separated at one time with a small force.

[Various Physical Properties of Adhesive Laminates]

The pressure-sensitive adhesive laminate of one embodiment of the present invention can be easily separated at one time with a small force at the interface P between the pressure-sensitive adhesive sheet (I) and the cured resin film-forming sheet (II) by the expansion treatment.

However, in the adhesive laminate of one embodiment of the present invention, after thermosetting the thermosetting resin layer (Z) to form a cured resin film, as an expansion treatment, the adhesive sheet (I) and the cured The peel force (F ₁ ) at the time of separation at the interface P between the cured resin films obtained by curing the thermosetting resin layer (Z) of the sheet (II) for forming a resin film is usually 0 to 2000 mN/25 mm, preferably 0 ~1000 mN/25mm, 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, still more preferably 0 to 50 mN/25 mm.

When the peeling force (F ₁ ) is 0 mN/25 mm, even if it is attempted to measure the peeling force by the method described in the examples, the peeling force may be too small to be measured.

In addition, the adhesive sheet (I) and the sheet for forming a cured resin film are preferred from the viewpoint that the sealing object is sufficiently fixed before the thermosetting of the thermosetting resin layer (Z) and the expansion treatment so as not to adversely affect the sealing operation. The adhesion between the thermosetting resin layers (Z) of (II) is high.

From the viewpoints described above, in the adhesive laminate according to one embodiment of the present invention, the adhesive sheet (I) and the cured resin film are formed for use in the adhesive sheet (I) before the thermosetting of the thermosetting resin layer (Z) and the expansion treatment. The peel force (F ₀ ) when the interface P of the thermosetting resin layer (Z) of the sheet (II) is separated is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, and further preferably 160 mN/25 mm or more. Preferably it is 50000mN/25mm or less.

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

The peeling force (F ₁ ) and the peeling force (F ₀ ) are the values measured by the method described in the examples.

In addition, as _a temperature condition at the time of measuring peeling force (F1), when using thermally expandable particle, what is necessary is just to set it as the expansion start temperature (t) or more of the thermally expandable particle.

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

In the pressure-sensitive adhesive laminate according to one embodiment of the present invention, the pressure-sensitive adhesive layer (X) (the first pressure-sensitive adhesive layer (X1) and the first pressure-sensitive adhesive layer (X1) and the first pressure-sensitive adhesive layer (X1) and 2 The adhesive force of the adhesive layer (X2)) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm, still more preferably 0.4 to 6.0 N/25 mm, still more preferably 0.5 to 4.0 N/25mm.

When the pressure-sensitive adhesive sheet (I) has the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) The adhesive force is preferably in the above-mentioned range, but from the viewpoint of improving the adhesion with the support and making it easier to realize separation at the interface P at one time, the second pressure-sensitive adhesive layer (X2) attached to the support is more preferred. The adhesive force of 1 is higher than that of the first adhesive layer (X1).

In addition, in the adhesive laminate of one embodiment of the present invention, from the viewpoint of making the adhesiveness with the sealing object good, the side where the sealing object is placed on the sheet (II) for forming a cured resin film is preferably surface is adhesive.

Specifically, it is preferable that it is 0.01-5 N/25mm, and, as for the adhesive force of the surface on the side where the sealing object of the sheet (II) for resin film formation is cured at room temperature (23° C.), it is preferably 0.01 to 5 N/25 mm, and more preferably 0.05 to 4 N/ 25mm, more preferably 0.1 to 3N/25mm.

However, when the sheet (II) for cured resin film formation consists only of the thermosetting resin layer (Z), it is sufficient to adjust the adhesive force of the surface of the thermosetting resin layer (Z) so that it may become the said range.

Moreover, when the sheet (II) for cured resin film formation has a thermosetting resin layer (Z) and an adhesive layer, what is necessary is just to adjust so that the adhesive force of an adhesive layer may become the said range.

In addition, in this specification, these adhesive force shows the value measured by the method as described in an Example.

The base material (Y) included in the pressure-sensitive adhesive sheet (I) is a non-adhesive base material.

In the present invention, when judging whether or not it is a non-adhesive base material, the base material is judged if the probe tack value measured based on JIS Z0237:1991 with respect to the surface of the target base material is less than 50 mN/5 mmφ. as "non-adhesive substrates".

The probe tack value of the surface of the base material (Y) of the PSA sheet (I) used in one embodiment of the present invention is generally less than 50 mN/5 mmφ, preferably less than 30 mN/5 mmφ, more preferably, independently of each other. It is less than 10mN/5mmφ, more preferably less than 5mN/5mmφ.

In addition, in this specification, the probe tack value of the surface of a base material shows the value measured by the method as described in an Example.

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

[Configuration of Adhesive Sheet (I)]

The pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate of the present invention has a base material (Y) and a pressure-sensitive adhesive layer (X), and is an expandable pressure-sensitive adhesive sheet including expandable particles in any layer.

Adhesion used in one embodiment of the present invention when the layer containing the expandable particles is contained in the structure of the base material (Y) and when it is contained in the structure of the pressure-sensitive adhesive layer (X) The sheet (I) can be classified as follows.

- Adhesive sheet (I) of 1st Embodiment: The adhesive sheet (I) provided with the base material (Y), and this base material (Y) has an expandable base material layer (Y1) containing an expandable particle.

Adhesive sheet (I) of the second embodiment: having a first adhesive layer (X1) as an expandable pressure-sensitive adhesive layer containing expandable particles on both sides of a base material (Y), and a non-expandable pressure-sensitive adhesive layer (X1) The pressure-sensitive adhesive sheet (I) of the second pressure-sensitive adhesive layer (X2) of the flexible pressure-sensitive adhesive layer.

<Adhesive Sheet (I) of First Embodiment>

As the PSA sheet (I) of the first embodiment, as shown in FIGS. 1 to 2 , there can be mentioned a PSA sheet in which the base material (Y) has an expandable base material layer (Y1) containing expandable particles.

In the pressure-sensitive adhesive sheet (I) of the first embodiment, the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive from the viewpoint that the interface P can be easily separated at one time with a small force Floor.

Specifically, in the pressure-sensitive adhesive sheet (I) included in the pressure-sensitive adhesive laminates 1 a and 1 b shown in FIG. 1 , the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer.

In addition, in the pressure-sensitive adhesive sheet (I) included in the pressure-sensitive adhesive laminates 2a and 2b shown in FIG. 2, it is preferable that both the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are non-expandable adhesive layer.

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

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

In addition, in this specification, when the pressure-sensitive adhesive sheet (I) has a plurality of pressure-sensitive adhesive layers as shown in FIG. 2, for example, the above-mentioned "thickness of the pressure-sensitive adhesive layer (X)" means The thickness of each adhesive layer (in FIG. 2, it is the thickness of each adhesive layer (X1) and (X2)).

In addition, in this specification, the thickness of each layer which comprises an adhesive laminated body shows the value measured by the method as described in an Example.

In the pressure-sensitive adhesive sheet (I) of the first embodiment, the thickness ratio [(Y1)/(X)] of the expandable base material layer (Y1) and the pressure-sensitive adhesive layer (X) before the expansion treatment is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, still more preferably 30 or less.

When the thickness ratio is 1000 or less, an adhesive that can be easily separated at one time with a small force at the interface P between the adhesive sheet (I) and the sheet for forming a cured resin film (II) by the expansion treatment can be obtained. Adhesive laminate.

In addition, this thickness ratio becomes like this. Preferably it is 0.2 or more, More preferably, it is 0.5 or more, More preferably, it is 1.0 or more, More preferably, it is 5.0 or more.

In addition, in the pressure-sensitive adhesive sheet (I) of the first embodiment, the base material (Y) may be formed of only the intumescent base material layer (Y1) as shown in FIG. 1( a ), or the form shown in FIG. As shown in 1(b), a form having an expandable base material layer (Y1) on the side of the sheet (II) for forming a cured resin film and a non-expandable base material layer (Y2) on the pressure-sensitive adhesive layer (X) side .

In the pressure-sensitive adhesive sheet (I) of the first embodiment, as the thickness ratio [(Y1)/(Y2)] of the expandable base material layer (Y1) and the non-expandable base material layer (Y2) before the expansion treatment, Preferably it is 0.02-200, More preferably, it is 0.03-150, More preferably, it is 0.05-100.

<Adhesive Sheet (I) of Second Embodiment>

As the PSA sheet (I) of the second embodiment, as shown in FIG. 3 , a first PSA having an expandable pressure-sensitive adhesive layer containing expandable particles on both sides of the base material (Y) can be exemplified. A layer (X1), and a pressure-sensitive adhesive sheet of the second pressure-sensitive adhesive layer (X2) as a non-expandable pressure-sensitive adhesive layer.

In addition, in the pressure-sensitive adhesive sheet (I) of the second embodiment, the first pressure-sensitive adhesive layer (X1) as an intumescent pressure-sensitive adhesive layer, and the thermosetting resin layer of the sheet (II) for forming a cured resin film (Z) Direct contact.

In addition, in the adhesive sheet (I) of 2nd Embodiment, it is preferable that a base material (Y) is a non-expandable base material. The non-expandable base material preferably consists of only the non-expandable base material layer (Y2).

In the pressure-sensitive adhesive sheet (I) of the second embodiment, the first pressure-sensitive adhesive layer (X1) as the expandable pressure-sensitive adhesive layer before the expansion treatment and the second pressure-sensitive adhesive layer as the non-expandable pressure-sensitive adhesive layer The thickness ratio [(X1)/(X2)] of the mixture layer (X2) is preferably 0.1 to 80, more preferably 0.3 to 50, and even more preferably 0.5 to 15.

Moreover, in the pressure-sensitive adhesive sheet (I) of the second embodiment, the thickness ratio of the first pressure-sensitive adhesive layer (X1) as the expandable pressure-sensitive adhesive layer before the expansion treatment to the base material (Y) [(X1 )/(Y1)], preferably 0.05-20, more preferably 0.1-10, still more preferably 0.2-3.

Hereinafter, the expandable particles that may be contained in any layer constituting the pressure-sensitive adhesive sheet (I) will be described, and on this basis, the expandable base material layer (Y1) and the non-expandable base material constituting the base material (Y) will be described. The material layer (Y2) and the adhesive layer (X) will be described in detail.

<Expandable particles>

The expandable particle used in the present invention may be any particle that is expanded by a predetermined expansion treatment.

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

In addition, the average particle diameter before expansion of the expansible particles is the volume median diameter (D ₅₀ ), and refers to the use of a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name “Mastersizer 3000”). In the measured particle distribution of the expandable particles before expansion, the cumulative volume frequency calculated from the particles with smaller particle diameters in the expandable particles before expansion corresponds to 50% of the particle diameter.

The 90% particle size (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, More preferably, it is 30-80 micrometers.

In addition, the 90% particle diameter (D90) before expansion of the expandable particle refers to the particle size before expansion measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name "Mastersizer 3000"). In the particle distribution of the expandable particles, the cumulative volume frequency calculated from the particles with smaller particle diameters in the expandable particles before expansion corresponds to 90% of the particle diameters.

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

The thermally expandable particles used in one embodiment of the present invention do not need to expand when the sealing material is cured, and may have an expansion initiation temperature (t) higher than the curing temperature of the sealing material. Specifically, expansion is preferred. The starting temperature (t) is adjusted to be thermally expandable particles of 60 to 270°C.

In addition, the expansion start temperature (t) can be suitably selected according to the curing temperature of the sealing material used.

In addition, in this specification, the expansion start temperature (t) of a thermally expandable particle shows the value measured by the following method.

(Measuring method of expansion start temperature (t) of thermally expandable particles)

0.5 mg of heat-expandable particles to be measured were placed in an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, and an aluminum cap (diameter 5.6 mm, thickness 0.1 mm) was placed on the cup to prepare a sample.

Using a dynamic viscoelasticity measuring apparatus, the height of the sample was measured in a state where a force of 0.01 N was applied to the sample from the upper part of the aluminum cover with an indenter. Then, in the state where a force of 0.01 N was applied by the indenter, the temperature was increased from 20°C to 300°C at a heating rate of 10°C/min, the displacement of the indenter in the vertical direction was measured, and the displacement in the positive direction was started. The temperature is taken as the expansion onset temperature (t).

The heat-expandable particles are preferably a microencapsulated foaming agent containing an outer shell formed of a thermoplastic resin, and an encapsulated component that is encapsulated by the outer shell and vaporized when heated to a predetermined temperature.

Examples of the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene Vinylidene chloride, polysulfone, etc.

Examples of the inner components enclosed in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, and isoheptane. , isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclopentane Tridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, isotridecane, 4-methyldodecane, Isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isononadecane, 2,6,10,14-Tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, Pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc.

These inner-package components may be used alone or in combination of two or more.

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

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

<Expandable base material layer (Y1)>

The expandable base material layer (Y1) of the pressure-sensitive adhesive sheet (I) used in one embodiment of the present invention contains expandable particles and can be expanded by a predetermined expansion treatment.

The content of the expandable particles in the expandable base layer (Y1) is preferably 1 to 40% by mass, and more preferably 5 to 35% by mass relative to the total mass (100% by mass) of the expandable base layer (Y1). , 10-30 mass % is more preferable, 15-25 mass % is still more preferable.

In addition, from the viewpoint of improving the interlayer adhesion between the intumescent substrate layer (Y1) and other layers to be laminated, the surface of the intumescent substrate layer (Y1) may be subjected to an oxidation method, Surface treatment such as concavo-convex method, adhesion-facilitating treatment, or primer treatment.

Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, and examples of the unevenness method include sandblasting, solvent processing, etc.

In one embodiment of the present invention, the expandable base material layer (Y1) is preferably a heat-expandable base material layer containing heat-expandable particles, and more preferably the heat-expandable base material layer satisfies the following condition (1).

· Condition (1): The storage elastic modulus E′(t) of the thermally expandable substrate layer is 1.0×10 ⁷ Pa or less at the expansion start temperature (t) of the thermally expandable particles.

In addition, in this specification, the storage elastic modulus E' of the thermally-expandable base material layer at a predetermined temperature shows the value measured by the method described in the Example.

The above-mentioned condition (1) may be an index representing the rigidity of the heat-expandable base material layer immediately before the expansion of the heat-expandable particles.

In order to easily separate the interface P between the adhesive sheet (I) and the cured resin film-forming sheet (II) with a small force, it is necessary to make the adhesive Concavities and convexities are easily formed on the surface of the laminate (I) on the side laminated with the thermosetting resin layer (Z).

That is, the heat-expandable base material layer satisfying the above-mentioned condition (1), at the expansion start temperature (t), the heat-expandable particles expand and become sufficiently large, and the thermosetting resin layer (Z) is easily laminated on the side. The surface of the pressure-sensitive adhesive sheet (I) has irregularities.

As a result, it is possible to obtain an adhesive laminate that can be easily separated by a small force at the interface P between the adhesive sheet (I) and the sheet for forming a cured resin film (II).

From the above viewpoints, the storage elastic modulus E'(t) of the thermally expandable base material layer specified in the condition (1) is preferably 9.0×10 ⁶ Pa or less, more preferably 8.0×10 ⁶ Pa or less, and still more preferably 6.0 ×10 ⁶ Pa or less, more preferably 4.0 × 10 ⁶ Pa or less, still more preferably 1.0 × 10 ⁶ Pa or less.

In addition, the flow of thermally expandable particles after expansion is suppressed, the shape retention of irregularities formed on the surface of the pressure-sensitive adhesive sheet (I) on the side where the thermosetting resin layer (Z) is laminated is improved, and the interface P is The storage elastic modulus E'(t) of the thermally expandable base material layer specified in the condition (1) is preferably 1.0×10 ³ Pa or more, more preferably 1.0, from the viewpoint of being able to separate more easily with a small force ×10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

The expandable base material layer (Y1) is preferably formed from the resin composition (y) containing a resin and expandable particles.

In addition, the resin composition (y) may contain the additive for base materials as needed in the range which does not impair the effect of this invention.

As a base material additive, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, etc. are mentioned, for example.

In addition, these base material additives may be used individually, respectively, and may be used in combination of 2 or more types.

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

About the expandable particle contained in the resin composition (y) which is the formation material of an expandable base material layer (Y1), as mentioned above, it is preferable that it is a thermally expandable particle.

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

The resin contained in the resin composition (y) as a material for forming the intumescent base layer (Y1) may be a non-adhesive resin or an adhesive resin.

That is, even if the resin contained in the resin composition (y) is an adhesive resin, as long as the adhesive resin and the polymerized The polymerizable compound undergoes a polymerization reaction, the obtained resin becomes a non-adhesive resin, and the expandable base material layer (Y1) containing the resin may be non-adhesive.

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

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

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

In addition, from the viewpoint of forming an intumescent base material layer (Y1) that satisfies the above-mentioned condition (1), the resin contained in the resin composition (y) preferably contains a resin selected from the group consisting of acrylic urethane-based resins and One or more of olefin resins.

Moreover, as said acrylic urethane resin, the following resin (U1) is preferable.

- Acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth)acrylate.

(Acrylic urethane resin (U1))

As a urethane prepolymer (UP) which forms the main chain of an acrylic urethane resin (U1), the reaction product of a polyhydric alcohol and a polyhydric isocyanate is mentioned.

In addition, it is preferable that a urethane prepolymer (UP) is a prepolymer obtained by further carrying out the chain extension reaction using a chain extension agent.

Examples of polyols used as raw materials for urethane prepolymers (UP) include alkylene polyols, ether polyols, ester polyols, ester amide polyols, and ester-ether polyols. Alcohols, 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, diols are preferred, ester diols, alkylene diols, and carbonate diols are more preferred, and ester diols and carbonates are still more preferred. type diol.

Examples of ester diols include polycondensates of one or two or more selected from the following diols and one or two or more selected from the following dicarboxylic acids and their acid anhydrides. Diols include: 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and other alkane diols, ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol and other alkylene glycols, etc.; the dicarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyl dicarboxylic acid Carboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chlorobridged acid, maleic acid, fumaric acid, itaconic acid, cyclohexane Alkane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid Formic acid, etc.

Specific examples include: polyethylene adipate diol, polybutylene adipate diol, poly-1,6-hexanediol adipate diol, poly-1,6-isophthalate diol Hexylene Glycol, Polyneopentyl Adipate Diol, Polyethylene Adipate Diol, Polyethylene Adipate Diol, Polybutylene Adipate Diol Diol 1,6-hexanediol ester diol, polyethylene glycol adipate diol, poly(polytetramethylene ether) adipate diol, poly(3-methyl adipate) pentanediol) diol, polyethylene azelaate diol, polyethylene sebacate diol, polybutylene azelaate diol, polybutylene sebacate diol Alcohol and polyneopentyl terephthalate diol, etc.

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

As carbonate-type diol, 1, 4- tetramethylene carbonate diol, 1, 5- pentamethylene carbonate diol, 1, 6- hexamethylene carbonate diol, 1,2-propylene carbonate diol, 1,3-propylene carbonate diol, 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol Alcohol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, etc.

As a polyvalent isocyanate used as a raw material of a urethane prepolymer (UP), aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned.

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

In addition, these polyvalent isocyanates may be trimethylolpropane adduct-type modified products, biuret-type modified products obtained by reacting with water, and isocyanurate-type modified products containing isocyanurate rings. sexual body.

Among these, the polyvalent isocyanate used in one embodiment of the present invention is preferably a diisocyanate, and more preferably selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate ( 2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and one or more of alicyclic diisocyanates.

Examples of alicyclic diisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, etc., preferably isocyanurate Phorone diisocyanate (IPDI).

In one embodiment of the present invention, the urethane prepolymer (UP) that forms the main chain of the acrylic urethane resin (U1) is preferably a reaction product of a diol and a diisocyanate, and has both ends of the urethane prepolymer (UP). Linear urethane prepolymers with ethylenically unsaturated groups.

As a method of introducing an ethylenically unsaturated group into both ends of the linear urethane prepolymer, there may be mentioned a method of reacting a diol and a diisocyanate compound at the ends of the linear urethane prepolymer. A method of reacting NCO groups with hydroxyalkyl (meth)acrylates.

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

At least (meth)acrylate is contained as a vinyl compound which forms the side chain of acrylic urethane resin (U1).

As the (meth)acrylate, at least one selected from the group consisting of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate is preferred, and alkyl (meth)acrylate and (meth)acrylate are more preferred. base) hydroxyalkyl acrylate used in combination.

In the case of using an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate in combination, as the amount of the hydroxyalkyl (meth)acrylate relative to 100 parts by mass of the alkyl (meth)acrylate The mixing ratio is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 30 parts by mass, still more preferably 1.0 to 20 parts by mass, still more preferably 1.5 to 10 parts by mass.

As carbon number of the alkyl group which this alkyl (meth)acrylate has, 1-24 are preferable, 1-12 are more preferable, 1-8 are still more preferable, and 1-3 are still more preferable.

In addition, as the hydroxyalkyl (meth)acrylate, the same as the above-mentioned hydroxyalkyl (meth)acrylate for introducing ethylenically unsaturated groups into both ends of the linear urethane prepolymer can be mentioned. of those.

Examples of vinyl compounds other than (meth)acrylates include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; methyl vinyl ether and ethyl vinyl ether. Isovinyl ethers; vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, (methyl) Monomers containing polar groups such as acrylamide; etc.

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

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

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

In the acrylic urethane-based resin (U1) used in one embodiment of the present invention, as the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (U11) derived from the vinyl compound The content ratio of u12) [(u11)/(u12)], in terms of mass ratio, is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, further preferably 30/70 to 60/ 40. More preferably, it is 35/65 to 55/45.

(olefin resin)

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

As said olefin monomer, a C2-C8 alpha-olefin is preferable, and ethylene, propylene, butene, isobutylene, 1-hexene, etc. are mentioned specifically,.

Among these, ethylene and propylene are preferable.

Specific olefin-based resins include, for example, ultra-low density polyethylene (VLDPE, density: 880 kg/m ³ or more and less than 910 kg/m ³ ), low density polyethylene (LDPE, density: 910 kg/m ³ or more and Less than 915kg/m ³ ), medium density polyethylene (MDPE, density: 915kg/m ³ or more and less than 942kg/m ³ ), high density polyethylene (HDPE, density: 942kg/m ³ or more), linear Polyethylene resins such as low density polyethylene; 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-based terpolymers such as ethylene-propylene-(5-ethylidene-2-norbornene); etc. Wait.

In one embodiment of the present invention, the olefin-based resin may be a modified olefin-based resin further modified at least one selected from the group consisting of acid modification, hydroxyl modification, and acrylic modification.

For example, examples of acid-modified olefin-based resins obtained by acid-modifying olefin-based resins include modified polymers obtained by graft-polymerizing unsaturated carboxylic acids or acid anhydrides thereof to the above-mentioned unmodified olefin-based resins. .

Examples of the above-mentioned unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaric acid, tetrahydrophthalic acid, aconitic acid, (methyl) ) acrylic acid, maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc.

In addition, an unsaturated carboxylic acid or its acid anhydride may be used individually, and may be used in combination of 2 or more types.

Examples of the acrylic-modified olefin-based resin obtained by acrylic-modifying the olefin-based resin include graft-polymerizing an alkyl (meth)acrylate as a side chain to the above-mentioned unmodified olefin-based resin as a main chain. modified polymer.

As carbon number of the alkyl group which the said alkyl (meth)acrylate has, 1-20 are preferable, 1-16 are more preferable, and 1-12 are still more preferable.

As the above-mentioned alkyl (meth)acrylate, for example, the same compounds as those which can be selected as the monomer (a1') described later can be mentioned.

Examples of the hydroxyl-modified olefin-based resin obtained by modifying the olefin-based resin with a hydroxyl group include a modified polymer obtained by graft-polymerizing a hydroxyl-containing compound to the above-mentioned unmodified olefin-based resin as the main chain.

Examples of the above-mentioned hydroxyl-containing compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. -Hydroxyalkyl (meth)acrylates such as hydroxybutyl, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol, etc. .

(Resins other than acrylic urethane resins and olefin resins)

In one embodiment of the present invention, resins other than the acrylic urethane-based resin and the olefin-based resin may be contained in the resin composition (y) within a range that does not impair the effects of the present invention.

Examples of such resins include vinyl-based resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalene. Polyester resins such as ethylene formate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane not belonging to acrylic urethane resins; polysulfone; Polyetheretherketone; polyethersulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; fluorine resins, etc.

Among them, from the viewpoint of forming an intumescent base material layer (Y1) that satisfies the above-mentioned condition (1), it is preferable that the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin in the resin composition (y) is small Case.

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

(Solventless resin composition (y1))

As the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a weight average molecular weight (Mw) of 50,000 or less, and an energy ray polymerizable monomer can be mentioned. , and a solvent-free resin composition (y1) in which the above-mentioned expandable particles are not compounded with a solvent.

Although no solvent is blended in the solvent-free resin composition (y1), the energy-ray polymerizable monomer contributes to the improvement of the plasticity of the oligomer.

By irradiating an energy ray to the coating film formed from the solvent-free resin composition (y1), it becomes easy to form the expandable base material layer (Y1) which satisfies the said condition (1).

In addition, the kind, shape, and compounding quantity (content) of the expandable particle compounded in the solvent-free resin composition (y1) are as described above.

The weight-average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, 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 it is 4000-30000.

In addition, as the oligomer, any oligomer having an ethylenically unsaturated group having a weight average molecular weight of 50,000 or less in the resin contained in the resin composition (y) may be used, and the above-mentioned urethane is preferred. Ester Prepolymer (UP).

In addition, as this oligomer, the modified olefin resin which has an ethylenically unsaturated group can also be used.

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

Examples of energy ray polymerizable monomers include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentenyloxy Alicyclic polymerizable compounds such as (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, and tricyclodecyl acrylate; phenylhydroxypropyl acrylate, benzyl acrylate, Aromatic polymerizable compounds such as phenol ethylene oxide modified acrylates; heterocyclic polymerizable compounds such as tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, etc. .

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

The compounding ratio of the oligomer and the energy ray polymerizable monomer (the 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 this invention, it is preferable that a photopolymerization initiator is further mix|blended with the solventless resin composition (y1).

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

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl phenyl sulfide. , tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, diacetyl, 8-chloroanthraquinone, etc.

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

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

<Non-expandable base material layer (Y2)>

As a material for forming the non-expandable base material layer (Y2) constituting the base material (Y), for example, paper, resin, metal, etc., can be mentioned, and can be changed according to the application of the adhesive laminate of one embodiment of the present invention. Choose appropriately.

As a paper material, tissue paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, cellophane, etc. are mentioned, for example.

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

As a metal, aluminum, tin, chromium, titanium etc. are mentioned, for example.

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

Examples of the non-expandable base material layer (Y2) using two or more forming materials in combination include a material obtained by laminating a paper material with a thermoplastic resin such as polyethylene, and a material formed on the surface of a resin film or sheet containing the resin. Materials made of metal films, etc.

In addition, as the formation method of the metal layer, for example, the method of vapor-depositing the above-mentioned metal by PVD methods such as vacuum evaporation, sputtering, and ion plating, or the method of pasting the above-mentioned metal using a conventional adhesive The method of metal foil, etc.

In addition, from the viewpoint of improving the interlayer adhesion between the non-expandable base material layer (Y2) and other layers to be laminated, when the non-expandable base material layer (Y2) contains a resin, The surface of the non-expandable base material layer (Y2) may be subjected to surface treatment, adhesion-facilitating treatment, or primer treatment by an oxidation method, a concavo-convex method, or the like similarly to the above-mentioned intumescent base material layer (Y1).

In addition, when the non-expandable base material layer (Y2) contains a resin, the above-mentioned base material additive which may be contained in the resin composition (y) may be further contained in addition to the resin.

The non-expandable base material layer (Y2) is a non-expandable layer that can be determined based on the above-mentioned method.

Therefore, the volume change rate (%) of the non-expandable base layer (Y2) which can be calculated by the above formula is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume, and even more preferably low It is less than 0.1 volume %, more preferably less than 0.01 volume %.

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

However, it is preferable that the content of the expandable particles in the non-expandable base material layer (Y2) is as small as possible.

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

<Adhesive layer (X)>

The pressure-sensitive adhesive layer (X) included in the pressure-sensitive adhesive sheet (I) used in one embodiment of the present invention may be formed of a pressure-sensitive adhesive composition (x) containing a pressure-sensitive adhesive resin.

Moreover, the adhesive composition (x) may contain additives for adhesives, such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, as needed.

Hereinafter, each component contained in the adhesive composition (x) will be described.

In addition, even when the pressure-sensitive adhesive sheet (I) has the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X1). The mixture layer (X2) may be formed from the 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 having adhesiveness alone and having a weight average molecular weight (Mw) of 10,000 or more.

The weight average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and further Preferably, it is 30,000 to 1,000,000.

Specific examples of adhesive resins include 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. resin, etc.

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

In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, and any of block copolymers, random copolymers, and graft copolymers may be used. form.

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

By forming an adhesive layer formed of a composition containing an energy ray-curable adhesive resin, the adhesive force can be reduced by irradiation with energy rays.

As this polymerizable functional group, a (meth)acryloyl group, a vinyl group, etc. are mentioned.

Moreover, as an energy ray, an ultraviolet-ray and an electron beam are mentioned, Preferably it is an ultraviolet-ray.

In addition, the composition containing the monomer or oligomer which has a polymerizable functional group may be sufficient as a formation material of the adhesive layer which can irradiate an energy ray and reduce adhesive force.

These compositions preferably further contain a photopolymerization initiator.

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

In addition, when using the adhesive sheet (I) which has the 1st adhesive layer (X1) and the 2nd adhesive layer (X2), by making the sheet (II) for cured resin film formation The first pressure-sensitive adhesive layer (X1) in contact contains an acrylic resin, and irregularities can be easily formed on the surface of the first pressure-sensitive adhesive layer.

The content ratio of the acrylic resin in the adhesive resin is preferably based on the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X). 30-100 mass %, More preferably, it is 50-100 mass %, More preferably, it is 70-100 mass %, More preferably, it is 85-100 mass %.

The content of the adhesive resin is preferably 35 to 100 mass %, more preferably 50 to 100 mass %, still more preferably 60 to 98 mass %, still more preferably 70 to 95 mass %.

(crosslinking agent)

In one Embodiment of this invention, when the adhesive composition (x) contains the adhesive resin which has a functional group, it is preferable to further contain a crosslinking agent.

This crosslinking agent is a component which reacts with the adhesive resin which has a functional group, and bridge|crosslinks adhesive resins with this functional group as a crosslinking origin.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned, for example.

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

Among these crosslinking agents, isocyanate-based crosslinking agents are preferred from the viewpoints of improving cohesive force and improving adhesive force, and from the viewpoints of availability and the like.

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

(Tackifier)

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

In this specification, "tackifier" refers to an oligomer having a weight-average molecular weight (Mw) of less than 10,000 among components that assist in improving the adhesive force of the above-mentioned adhesive resin, and is distinguished from the above-mentioned adhesive composition of resin.

The weight average molecular weight (Mw) of the tackifier 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, pentene produced by thermal decomposition of naphtha, isoprene, piperine, and 1,3-pentanediol. C5-based petroleum resins obtained by copolymerization of C5 fractions such as alkene, C9-based petroleum resins obtained by copolymerization of C9 fractions such as indene and vinyltoluene generated by thermal decomposition of naphtha, and hydrogenated resins obtained by hydrogenation of these resins Wait.

The softening point of the tackifier is preferably 60 to 170°C, more preferably 65 to 160°C, further preferably 70 to 150°C.

In addition, in this specification, the "softening point" of a tackifier shows the value measured based on JISK2531.

The tackifier may be used alone or in combination of two or more having different softening points, structures, and the like.

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

The content of the tackifier is preferably 0.01 to 65 mass % with respect to the total mass (100 mass %) of the active ingredients of the adhesive composition (x) or the total mass (100 mass %) of the adhesive layer (X) , 0.1-50 mass % is more preferable, 1-40 mass % is further more preferable, 2-30 mass % is still more preferable.

(Photopolymerization initiator)

In one embodiment of the present invention, 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 In the case of a compound, the composition preferably further contains a photopolymerization initiator.

By containing a photoinitiator, even if it irradiates the energy ray of low energy, a hardening reaction can fully progress.

In addition, as a photoinitiator, the thing similar to what was mix|blended with the above-mentioned solventless resin composition (y1) is mentioned.

The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass relative to 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 The mass part is more preferably 0.05 to 2 mass parts.

(Additives for Adhesives)

In one embodiment of the present invention, the adhesive composition (x) may contain, in addition to the above-mentioned additives, additives for adhesives used in conventional adhesives within a range that does not impair the effects of the present invention .

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

In addition, these additives for binders may be used individually, respectively, and may be used in combination of 2 or more types.

When these additives for adhesives are contained, it is preferable that content of each additive for adhesives is 0.0001-20 mass parts with respect to 100 mass parts of adhesive resins, More preferably, it is 0.001-10 mass parts.

In addition, when using the pressure-sensitive adhesive sheet (I) of the above-mentioned second embodiment having the first pressure-sensitive adhesive layer (X1) as the expandable pressure-sensitive adhesive layer, as the expandable pressure-sensitive adhesive layer, That is, the material for forming the first pressure-sensitive adhesive layer (X1) can be formed from an expandable pressure-sensitive adhesive composition (x11) in which expandable particles are further contained in the pressure-sensitive adhesive composition (x) described above.

The expandable particles are as described above.

The content of the expandable particles is preferably 1 to 70 mass %, More preferably, it is 2-60 mass %, More preferably, it is 3-50 mass %, More preferably, it is 5-40 mass %.

On the other hand, when the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer, the higher the content of the expandable particles in the pressure-sensitive adhesive composition as a material for forming the non-expandable pressure-sensitive adhesive layer As few as possible are preferred.

The content of the expandable particles in the pressure-sensitive adhesive composition (x), which is the material for forming the non-expandable pressure-sensitive adhesive layer, is based on the total amount (100 mass %) of the active ingredients in the pressure-sensitive adhesive composition (x). ) or the total mass (100 mass %) of the adhesive layer (X) is preferably less than 1 mass %, more preferably less than 0.1 mass %, further preferably less than 0.01 mass %, still more preferably less than 0.001 mass %.

In addition, as in the adhesive laminated bodies 2a and 2b shown in FIG. 2, the 1st adhesive layer (X1) and the 2nd adhesive layer (X1) which are non-expandable adhesive layers are used. In the case of the pressure-sensitive adhesive sheet (I) of X2), the shear storage elastic modulus G' (23) at 23°C of the first pressure-sensitive adhesive layer (X1) as a non-expandable pressure-sensitive adhesive layer is preferably 1.0 ×10 ⁸ Pa or less, more preferably 5.0 × 10 ⁷ Pa or less, still more preferably 1.0 × 10 ⁷ Pa or less.

When the shear storage elastic modulus G' (23) of the first pressure-sensitive adhesive layer (X1) as the non-expandable pressure-sensitive adhesive layer is 1.0×10 ⁸ Pa or less, for example, in the adhesive lamination shown in FIG. 2 In the case of the structures like bodies 2a and 2b, the first pressure-sensitive adhesive layer that is in contact with the sheet (II) for forming a cured resin film is easily formed by the expansion of the expandable particles in the expandable base material layer (Y1) by the expansion treatment. The surface of (X1) has irregularities.

As a result, an adhesive laminate which can be easily separated at one time with a small force at the interface P of the adhesive sheet (I) and the sheet for forming a cured resin film (II) can be obtained.

In addition, the shear storage elastic modulus G'(23) at 23 degreeC of the 1st pressure-sensitive adhesive layer (X1) which is a non-expandable pressure-sensitive adhesive layer is preferably 1.0×10 ⁴ Pa or more, more preferably 1.0×10 4 Pa or more 5.0×10 ⁴ Pa or more, more preferably 1.0×10 ⁵ Pa or more.

[Configuration of Sheet (II) for Forming Cured Resin Film]

The sheet (II) for cured resin film formation which the adhesive laminated body of this invention has is a material which 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 structure composed of only the thermosetting resin layer (Z), or may be provided on one surface side of the thermosetting resin layer (Z). Multilayer structure with other layers.

In addition, in the sheet (II) for forming a cured resin film used in one embodiment of the present invention, another layer is provided on one surface side of the thermosetting resin layer (Z), but the thermosetting resin layer (Z) ) is directly laminated with the pressure-sensitive adhesive sheet (I) without providing another layer.

Among them, in the sheet (II) for forming a cured resin film used in one embodiment of the present invention, a pressure-sensitive adhesive layer may be further provided on one surface side of the thermosetting resin layer (Z), and the thermosetting resin layer may be formed (Z) has a non-thermosetting base material layer between it and the above-mentioned pressure-sensitive adhesive layer.

The said adhesive layer can be formed from the adhesive composition (x) which is the formation material of the said adhesive layer (X). In addition, the above-mentioned non-thermosetting base material layer can also be formed from the same forming material as the above-mentioned non-expandable base material layer (Y2).

Hereinafter, the thermosetting resin layer (Z) which the sheet (II) for cured resin film formation has is demonstrated.

<Thermosetting resin layer (Z)>

The thermosetting resin layer (Z) only needs to be formed of a composition capable of forming a cured resin film by thermosetting, and it is possible to obtain a cured sealing body with a cured resin film having a flat surface with suppressed warpage. From the viewpoint of an adhesive laminate, it is preferably a layer formed from a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B).

In addition, the thermosetting composition (z) may further contain at least one selected from the group consisting of a colorant (C), a coupling agent (D), and an inorganic filler (E). From the above-mentioned viewpoints, it is preferable to contain at least one Inorganic filler material (E).

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

From the viewpoint of obtaining an adhesive laminate capable of producing a cured seal body with a cured resin film having a flat surface with suppressed warpage, the cured resin film obtained by thermosetting the thermosetting resin layer (Z) was heated at 23° C. The storage elastic modulus E' of the lower limit is preferably 1.0×10 ⁷ Pa or more, more preferably 1.0×10 ⁸ Pa or more, still more preferably 1.0×10 ⁹ Pa or more, still more preferably 5.0×10 ⁹ Pa or more, and It is preferably 1.0×10 ¹³ Pa or less, more preferably 1.0×10 ¹² Pa or less, still more preferably 5.0×10 ¹¹ Pa or less, still more preferably 1.0×10 ¹¹ Pa or less.

Hereinafter, the various components contained in the thermosetting composition (z) as a forming material of the thermosetting resin layer (Z) will be described.

(polymer component (A))

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

By containing the polymer component (A) in the formed thermosetting resin layer (Z), flexibility and film-forming properties can be imparted to the thermosetting resin layer (Z), and the sheet properties can be maintained well.

The weight average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, still more preferably 50,000 to 2,000,000, still more preferably 100,000 to 1,500,000, and even more preferably More preferably, it is 200,000 to 1,000,000.

The content of the component (A) is preferably 5 to 50 mass %, more preferably 5 to 50 mass %, relative to the total mass (100 mass %) of the active ingredients of the thermosetting composition (z) or the total mass (100 mass %) of the thermosetting resin layer (Z). Preferably it is 8-40 mass %, More preferably, it is 10-30 mass %.

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

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

It should be noted that in this specification, the acrylic polymer having an epoxy group and the phenoxy resin having an epoxy group are thermosetting, but these resins have a weight average molecular weight of 20,000 or more and have at least A compound of a repeating unit is considered to be included in the concept of the polymer component (A).

Among these, it is preferable that the polymer component (A) contains the 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 % with respect to the total amount (100 mass %) of the polymer component (A). %, more preferably 80 to 100 mass %, still more preferably 90 to 100 mass %.

(acrylic polymer (A1))

From the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer (Z), the weight average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3 million, more preferably 100,000 to 1.5 million, More preferably, it is 150,000 to 1,200,000, and still more preferably 250,000 to 1,000,000.

From the viewpoint of imparting good adhesiveness to the surface of the thermosetting resin layer (Z), and from the viewpoint of improving the reliability of the cured sealing body with the cured resin film produced using the adhesive laminate, the acrylic polymer (A1 ), the glass transition temperature (Tg) is preferably -60 to 50°C, more preferably -50 to 30°C, still more preferably -40 to 10°C, and still more preferably -35 to 5°C.

Examples of the acrylic polymer (A1) include polymers containing alkyl (meth)acrylates as a main component, and specifically, those containing (methyl) derived from an alkyl group having 1 to 18 carbon atoms are preferred. ) An acrylic polymer of the structural unit (a1) of an alkyl acrylate (a1') (hereinafter also referred to as "monomer (a1')"), more preferably an acrylic polymer containing the structural unit (a1) and a The acrylic copolymer of the structural unit (a2) of a functional group monomer (a2') (henceforth "monomer (a2')").

The acrylic polymer (A1) may be used alone or in combination of two or more.

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

From the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer (Z), the number of carbon atoms of the alkyl group contained in the monomer (a1') is preferably 1 to 18, more preferably 1 to 12, and still more preferably 1 to 8. 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.

The monomer (a1') preferably contains an alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms, from the viewpoint of improving the reliability of the cured sealing body with a cured resin film produced using the adhesive laminate. base ester, more preferably contains methyl (meth)acrylate.

From the above-mentioned viewpoint, the structural unit (a11) derived from the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms relative to all the structural units (100% by mass) of the acrylic polymer (A1). ) is preferably 1 to 80 mass %, more preferably 5 to 80 mass %, further preferably 10 to 80 mass %.

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

From the viewpoints described above, (methyl) derived from an alkyl group having 4 or more carbon atoms (preferably 4 to 6, more preferably 4) with respect to all structural units (100% by mass) of the acrylic polymer (A1). 1-70 mass % is preferable, as for content of the structural unit (a12) of alkyl) acrylate, 5-65 mass % is more preferable, 10-60 mass % is further more preferable.

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

The monomer (a2') is preferably at least one selected from a hydroxyl group-containing monomer and an epoxy group-containing monomer.

It should be noted that the monomer (a2') may be used alone or in combination of two or more.

As a hydroxyl group-containing monomer, those same as the above-mentioned hydroxyl-containing compound are mentioned, Preferably it is hydroxyalkyl (meth)acrylate, More preferably, it is 2-hydroxyethyl (meth)acrylate.

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

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

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

In addition, the acrylic polymer (A1) may have a structural unit derived from another monomer other than the said structural unit (a1) and (a2) in the range which does not impair the effect of this invention.

As other monomers, vinyl acetate, styrene, ethylene, α-olefin, etc. are mentioned, for example.

<Thermosetting component (B)>

The thermosetting component (B) functions to thermoset the thermosetting resin layer (Z) to form a hard cured resin film, and is a compound having a weight average molecular weight of less than 20,000.

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

As the thermosetting component (B), it is preferable to contain an epoxy compound which is a compound having an epoxy group from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface (B1) and the thermosetting agent (B2), it is more preferable to further contain a curing accelerator (B3) together with the epoxy compound (B1) and the thermosetting agent (B2).

Examples of the epoxy compound (B1) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolak epoxy resins, and dicyclopentadiene epoxy resins. , Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other epoxy compounds with more than 2 functions in the molecule and a weight average molecular weight of less than 20,000 Wait.

The epoxy compound (B1) may be used alone or in combination of two or more.

Content of epoxy compound (B1) with respect to 100 parts by mass of polymer component (A) from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface Preferably it is 1-500 mass parts, More preferably, it is 3-300 mass parts, More preferably, it is 10-150 mass parts, More preferably, it is 20-120 mass parts.

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

As a thermosetting agent, the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is preferable.

As this functional group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid anhydride, etc. are mentioned. Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable, and a phenolic hydroxyl group or an amino group is more preferable from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface. , more preferably an amino group.

Examples of the phenolic thermosetting agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, XYLOK-type phenolic resins, and aralkylphenolic resins.

As an amine thermosetting agent which has an amino group, dicyandiamide (DICY) etc. are mentioned, for example.

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

Content of thermosetting agent (B2) with respect to 100 parts by mass of epoxy compound (B1) from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface Preferably it is 0.1-500 mass parts, More preferably, it is 1-200 mass parts.

The curing accelerator (B3) is a compound having a function of increasing the thermosetting speed when thermosetting the thermosetting resin layer (Z).

Examples of the curing accelerator (B3) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy Imidazoles such as methylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; .

These curing accelerators (B3) may be used alone or in combination of two or more.

From the viewpoint of obtaining an adhesive laminated body capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface, relative to 100 mass of the total amount of epoxy compound (B1) and thermosetting agent (B2) parts, 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, still more preferably 0.3 to 4 parts by mass.

<Colorant (C)>

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

When the thermosetting resin layer (Z) formed from the thermosetting composition (z) containing the colorant (C) is thermally cured to obtain a cured resin film, the cured resin film can shield infrared rays and the like generated from peripheral devices to prevent sealing objects Malfunction of objects (semiconductor chips, etc.).

As the colorant (C), organic or inorganic pigments and dyes can be used.

As the dye, any of acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes, and the like can be used.

Moreover, it does not specifically limit as a pigment, It can select and use suitably from well-known pigments.

Among these, black pigments are preferable from the viewpoints of good shielding properties against electromagnetic waves and infrared rays and further improvement in visibility by laser marking.

Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon. From the viewpoint of improving the reliability of the semiconductor chip, carbon black is preferred.

In addition, these coloring agents (C) may be used individually and may be used in combination of 2 or more types.

The content of the component (C) is preferably 0.1 to 30% by mass, more preferably 0.1 to 30% by mass, relative to the total mass (100% by mass) of the active ingredients of the thermosetting composition (z) or the total mass (100% by mass) of the thermosetting resin layer (Z). Preferably it is 0.5-25 mass %, More preferably, it is 1.0-15 mass %, More preferably, it is 1.2-5 mass %.

<Coupling agent (D)>

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

The thermosetting resin layer (Z) formed from the thermosetting composition (z) containing the coupling agent (D) can improve the adhesiveness with the sealing object. Moreover, with respect to the cured resin film obtained by thermosetting the thermosetting resin layer (Z), the water resistance can be improved without impairing the heat resistance.

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

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyl diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(methacryloyloxypropyl)trimethoxysilane, 3-aminopropyltrimethoxysilane Silane, N-6-(aminoethyl)-3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl- 3-aminopropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethyl) oxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, and the like.

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 15000, more preferably 125 to 10000, more preferably 150 to 5000, still more preferably 175 to 3000, still more preferably 200 to 2000.

The content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, relative to the total mass (100% by mass) of the active ingredients of the thermosetting composition (z) or the total mass (100% by mass) of the thermosetting resin layer (Z). Preferably it is 0.05-7 mass %, More preferably, it is 0.10-4 mass %, More preferably, it is 0.15-2 mass %.

<Inorganic Filler (E)>

The thermosetting composition (z) used in one embodiment of the present invention preferably further contains an inorganic Filler (E).

For the thermosetting resin layer (Z) formed from the thermosetting composition (z) containing the inorganic filler (E), the degree of thermosetting of the thermosetting resin layer (z) can be adjusted when thermosetting the sealing material , so that the difference in shrinkage stress between the two surfaces of the cured sealing body is reduced. As a result, it is possible to suppress the warpage and obtain a cured sealing body with a cured resin film having a flat surface.

Moreover, the thermal expansion coefficient of the cured resin film obtained by thermosetting the thermosetting resin layer (Z) can be adjusted to an appropriate range, and the reliability of the object to be sealed can be improved. In addition, the moisture absorption rate of the cured resin film can also be reduced.

The inorganic filler (E) may be any non-expandable material, for example, powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, etc., Non-thermally expandable particles such as beads, single crystal fibers, and glass fibers obtained by spheroidizing these.

These inorganic fillers (E) may be used alone or in combination of two or more.

Among these, from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface, silica or alumina is preferred.

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

From the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin film having a flat surface, the total amount (100% by mass) of active ingredients relative to the thermosetting composition (z) or The total mass (100 mass %) of the thermosetting resin layer (Z) and the content of the component (E) are preferably 25 to 80 mass %, more preferably 30 to 70 mass %, further preferably 40 to 65 mass %, still more preferably It is 45-60 mass %.

<Other additives>

The thermosetting composition (z) used in one embodiment of the present invention may further contain other additives other than the above-mentioned components (A) to (E) within a range that does not impair the effects of the present invention.

As other additives, a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a getter, a chain transfer agent, etc. are mentioned, for example.

However, as the total content of other additives other than components (A) to (E), relative to the total amount (100 mass %) of the active ingredients in the thermosetting composition (z) or the total mass (100 mass %) of the thermosetting resin layer (Z) mass %), preferably 0 to 20 mass %, more preferably 0 to 10 mass %, still more preferably 0 to 5 mass %.

[How to use the adhesive laminate]

The adhesive laminate of the present invention can be easily separated from the support at one time with a small force after the sealing process can be performed by fixing the object to be sealed to the support body. Moreover, by using this adhesive laminated body, productivity can be improved, and the cured sealing body with a cured resin film which has a flat surface with suppressed curvature can be manufactured.

Therefore, in the adhesive laminate of the present invention, the following methods of use are preferred:

The object to be sealed is placed on the surface of the sheet (II) for forming a cured resin film, the object to be sealed and at least the surface of the sheet (II) for forming a cured resin film of the peripheral portion of the object to be sealed are covered with a sealing material , the sealing material is thermally cured to form a cured sealing body containing the above-mentioned sealing object.

In addition, in the above-mentioned usage method, it is preferable to use as follows: when the above-mentioned sealing material is cured, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, and at the same time, by making the above-mentioned expansion It is separated at the interface P by the treatment of the expansion of the natural particles, and a cured sealing body with a cured resin film is obtained.

By using the adhesive laminate of the present invention as described above, it is possible to improve productivity and to manufacture a cured seal body with a cured resin film having a flat surface with suppressed warpage.

It should be noted that, in the above-mentioned method of use, the preferred configuration of the adhesive laminate is as described above, and the type of sealing material, the method of coating the sealing material, various conditions for thermal curing, etc. are as follows. It is as described in the item of "the manufacturing method of the cured sealing body with a cured resin film".

[Manufacturing method of cured sealing body with cured resin film]

As a method of producing a cured sealing body with a cured resin film using the adhesive laminate of the present invention, a method including the following steps (i) to (iii) can be mentioned.

Step (i): The adhesive surface of the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet (I) included in the pressure-sensitive adhesive laminate is affixed to the support, and the adhesive layer (II) of the sheet (II) for forming a cured resin film is attached to the adhesive surface. A step of placing an object to be sealed on a part of the surface.

Step (ii): Covering the object to be sealed and the surface of the sheet (II) for forming a cured resin film in at least a peripheral portion of the object to be sealed with a sealing material, and thermally curing the sealing material to form a composition comprising the A step of forming a cured resin film by thermally curing the thermosetting resin layer (Z) at the same time as the cured sealing body of the sealing object.

- Process (iii): the process of obtaining the cured sealing body with a cured resin film by separating the said adhesive laminated body at the interface P by the process which expands the said expandable particle.

Fig. 4 is a schematic cross-sectional view showing a process for producing a cured sealing body with a cured resin film using the adhesive laminate 1a shown in Fig. 1(a). Hereinafter, each of the above-mentioned steps will be described with reference to FIG. 4 as appropriate.

<Process (i)>

The step (i) is to attach the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) included in the adhesive laminate to a support, and attach it to the surface of the sheet (II) for forming a cured resin film. A step of placing the object to be sealed in a part of it.

FIG. 4( a ) shows that the adhesive layer (X) of the adhesive sheet (I) is adhered to the support 50 using the adhesive laminate 1 a in this step, and the adhesive layer (X) of the adhesive sheet (I) is used for forming a cured resin film. A state in which the sealing object 60 is placed on a part of the surface of the thermosetting resin layer (Z) of the sheet (II).

In addition, although the example using the adhesive laminated body 1a shown in FIG.1(a) is shown in FIG.4(a), the adhesive laminated body of this invention which has another structure is used. Also in the case of , the above-mentioned support body, the above-mentioned adhesive laminated body, and the above-mentioned sealing object are similarly laminated or placed in this order.

As temperature conditions in the step (i), it is preferable to perform at a temperature at which the expandable particles do not expand.

For example, in the case of using thermally expandable particles as the expandable particles, the temperature may be lower than the expansion initiation temperature (t) of the thermally expansible particles, but it is preferably in an environment of 0 to 80°C (at the expansion initiation temperature (t). When t) is 60-80 degreeC, it is performed in the environment lower than the expansion start temperature (t).

The above-mentioned support is preferably attached to the entire adhesive surface of the adhesive layer (X) of the adhesive laminate.

Therefore, the support body is preferably in the shape of a plate. Moreover, as shown in FIG. 4, it is preferable that the area of the surface of the support body which adheres to the adhesive surface of the adhesive layer (X) is equal to or larger than the area of the adhesive surface of the adhesive layer (X).

The material constituting the support body can be appropriately selected in consideration of required properties such as mechanical strength and heat resistance, depending on the type of the object to be sealed, the type of sealing material used in the step (ii), and the like.

Specific examples of the material constituting the support include metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resins, ABS resins, acrylic resins, engineering plastics, special engineering plastics, and polyimide resins , resin materials such as polyamide-imide resins; composite materials such as glass epoxy resins, etc. Among these, SUS, glass, and silicon wafers are preferred.

In addition, as an engineering plastics, nylon, polycarbonate (PC), polyethylene terephthalate (PET), etc. are mentioned.

As special engineering plastics, polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), etc. are mentioned.

The thickness of the support body can be appropriately selected depending on the type of the object to be sealed, the type of the sealing material used in the step (ii), and the like, but is preferably 20 μm or more and 50 mm or less, and more preferably 60 μm or more and 20 mm or less.

On the other hand, as a sealing object to be mounted on a part of the surface of the sheet (II) for forming a cured resin film, for example, semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic parts, sapphire substrates, and displays can be mentioned. , Panel substrates, etc.

For example, when the object to be sealed is a semiconductor chip, by using the adhesive laminate of the present invention, a semiconductor chip with a cured resin film can be produced.

As the semiconductor chip, conventionally known ones can be used, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface thereof.

Moreover, it is preferable to mount a semiconductor chip so that the back surface on the opposite side to a circuit surface may be covered with the surface of the sheet (II) for cured resin film formation. In this case, after mounting, the circuit surface of the semiconductor chip is exposed.

For mounting the semiconductor chip, a known device such as a flip chip bonder and a die bonder can be used.

The layout of the arrangement of the semiconductor chips, the number of arrangements, and the like may be appropriately determined according to the form of the target package, the number of production, and the like.

Here, it is preferably applied to a semiconductor chip, such as FOWLP, FOPLP, etc., in which a region larger than the chip size is covered with a sealing material to form a rewiring layer not only on the circuit surface of the semiconductor chip, but also on the surface region of the sealing material. Encapsulation of wiring layers.

Therefore, the semiconductor chip is placed on a part of the surface of the curable resin layer (I). Preferably, a plurality of semiconductor chips are placed on the surface in a state of being arranged with a certain interval therebetween, and more preferably a plurality of semiconductor chips are placed at a certain interval. And a matrix-like state arranged in a plurality of rows and columns is placed on the surface.

The space|interval of a semiconductor chip can be suitably determined according to the form etc. of the target package.

<Process (ii)>

The step (ii) is to coat the above-mentioned object to be sealed and the above-mentioned surface of the sheet (II) for forming a cured resin film in at least a peripheral portion of the object to be sealed with a sealing material (hereinafter, also referred to as "coating treatment"), so that A step of forming a cured resin film by thermally curing the sealing material (hereinafter also referred to as "thermosetting treatment") to form a cured sealing body including the above-mentioned sealing object, and also thermally curing the thermosetting resin layer (Z).

In the coating treatment of the step (ii), first, the object to be sealed and at least the peripheral portion of the object to be sealed on the surface of the sheet (II) for forming a cured resin film are coated with a sealing material.

The sealing material covers the entire exposed surface of the sealing object, and also fills the gaps between the plurality of semiconductor chips.

For example, FIG.4(b) shows the state covered with the sealing material so that the surface of the sealing object 60 and the sheet (II) for cured resin film formation may be completely covered.

The sealing material has a function of protecting the sealing object and its accompanying components from the external environment.

The sealing material used in the production method of the present invention is a thermosetting sealing material containing a thermosetting resin.

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

The coating method can be appropriately selected from methods used in the conventional sealing process according to the type of the sealing material. For example, a roll lamination method, a vacuum pressing method, a vacuum lamination method, a spin coating method, and a die coating method can be used. , transfer molding, compression molding, etc.

Furthermore, after performing the coating process, the sealing material is thermally cured to obtain a cured sealing body in which the sealing object is sealed by the sealing material.

In addition, the coating treatment and the thermosetting treatment of the step (ii) are performed at a temperature at which the expandable particles do not expand. For example, when an adhesive laminate having a layer containing heat-expandable particles is used, It is preferable to carry out under temperature conditions lower than the expansion start temperature (t) of this heat-expandable particle.

In addition, the coating process and the thermosetting process may be carried out separately, but when the sealing material is heated in the coating process, the sealing material may be directly thermosetted by the heating, and the coating process and the thermosetting process may be carried out simultaneously. Thermal curing process.

In this step, the thermosetting resin layer (Z) is also thermally cured at the same time as the thermal curing treatment of the sealing material to form a cured resin film.

In the manufacturing method of this invention, as shown in FIG.4(b), thermosetting process is performed in the state which provided the thermosetting resin layer (Z) on the sealing object 60 side sealed with the sealing material 70.

It is considered that since the thermosetting resin layer (Z) is provided, the difference in shrinkage stress between the two surfaces of the obtained cured seal body can be reduced, and the warpage generated in the cured seal body can be effectively suppressed.

<Process (iii)>

The step (iii) is a step of obtaining a cured sealing body with a cured resin film by separating at the interface P by the treatment of expanding the expandable particles.

FIG. 4( c ) shows a state in which separation is performed at the interface P by the process of expanding the expandable particles.

As shown in FIG. 4( c ), by separating at the interface P, a cured sealing body 80 in which the sealing object 60 is sealed and a cured resin in which the thermosetting resin layer (Z) is thermally cured can be obtained. Cured sealing body 100 with cured resin film of film (Z').

It should be noted that the presence of the cured resin film (Z') has the function of effectively suppressing the warpage generated in the cured sealing body, and also protects the sealing object and contributes to the improvement of the reliability of the sealing object.

The "treatment to expand ..." in the step (iii) is a treatment performed according to the type of expandable particles to be used.

For example, when heat-expandable particles are used, the heat-expandable particles are expanded by heating above the heat-expansion initiation temperature (t), whereby the adhesive sheet (II) on the side of the cured resin film-forming sheet (II) is I) has unevenness on the surface. As a result, the separation at the interface P can be easily performed at one time with a small force.

As the "temperature not less than the expansion start temperature (t)" when the heat-expandable particles are expanded, the "expansion start temperature (t)+10°C" or more and the "expansion start temperature (t)+60°C" or less are preferred. , more preferably "expansion initiation temperature (t)+15°C" or more and "expansion initiation temperature (t)+40°C" or less.

In addition, from the viewpoint of facilitating separation at the interface P between the adhesive sheet (I) and the cured resin film-forming sheet (II), the heat source during heating is preferably provided on the support side.

The cured sealing body with the cured resin film thus obtained may be subjected to a step of grinding the cured sealing body until the circuit surface of the semiconductor chip is exposed, rewiring the circuit surface, or forming external electrode pads. Steps such as connecting the external electrode pads to the external terminal electrodes.

In addition, after connecting the external terminal electrodes to the cured sealing body, the cured sealing body may be separated into pieces to manufacture a semiconductor device.

Example

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

<Weight Average Molecular Weight (Mw)>

The value measured under the following conditions using a gel permeation chromatography apparatus (manufactured by Tosoh Corporation, product name "HLC-8020") and measured in terms of standard polystyrene was used.

(measurement conditions)

Column: "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", and "TSK gel G1000HXL" (all manufactured by Tosoh Corporation) connected in sequence

·Column temperature: 40℃

Developing solvent: tetrahydrofuran

·Flow rate: 1.0mL/min

<Measurement of Thickness of Each Layer>

The measurement was performed using a constant pressure thickness gauge (model: "PG-02J", standard: based on JIS K6783, Z1702, Z1709) manufactured by TECLOCK.

<Storage modulus E' of intumescent base material layer (Y1)>

The formed intumescent base material layer (Y1) was made into a size of 5 mm in length x 30 mm in width x 200 μm in thickness, and after removing the peeling material, the obtained material was used as a test sample.

Using a dynamic viscoelasticity measuring device (manufactured by TA INSTRUMENTS, product name "DMAQ800"), 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. The storage modulus E' of the test sample at a given temperature.

<Shear storage modulus G' of adhesive layers (X1) and (X2)>

The formed pressure-sensitive adhesive layers (X1) and (X2) were cut into circles with a diameter of 8 mm, and then the release material was removed and stacked to prepare a sample with a thickness of 3 mm, and this sample was used as a test sample.

Using a viscoelasticity measuring apparatus (manufactured by Anton Paar, apparatus name "MCR300"), 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, the torsional shear method was used to measure The shear storage modulus G' of the test sample at a given temperature is calculated.

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

After laminating the thermosetting resin layer (Z) to a thickness of 200 μm, it was placed in an oven in a nitrogen atmosphere and heated at 130° C. for 2 hours to thermoset the thermosetting resin layer (Z) having a thickness of 200 μm to obtain a cured resin film.

Using a dynamic viscoelasticity measuring device (manufactured by TA INSTRUMENTS, product name "DMAQ800"), all samples were 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. Storage modulus E' of the formed cured resin film at 23°C.

<Probe stickiness value>

After cutting the base material to be measured into a square with a side length of 10 mm, it was left to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity), and the obtained sample was used as a test sample.

In an environment of 23°C and 50% RH (relative humidity), the probe adhesion tester (manufactured by Tester Sangyo Co., Ltd., product name "TE-6001") was used to measure the adhesion of the surface of the test sample based on JIS Z0237:1991. Needle stickiness value.

Specifically, after a stainless steel probe having a diameter of 5 mm was brought into contact with the surface of the test sample at a contact load of 0.98 N/cm ² for 1 second, the probe was separated from the surface of the test sample at a speed of 10 mm/sec. The required force was used as the probe tack value of the test sample.

<Measurement of Adhesive Strength>

On the surface of the thermal adhesive layer or thermosetting resin layer (Z) formed on the release film, a PET film (manufactured by Toyobo Co., Ltd., product name "COSMOSHINE A4100") having a thickness of 50 μm was laminated.

Then, the release film was removed, and the exposed surface of the pressure-sensitive adhesive layer or thermosetting resin layer (Z) was attached to a stainless steel plate (SUS304 No. 360 polishing) as an adherend, and the temperature was 23°C, 50% RH (relative humidity) After standing for 24 hours in the same environment, based on JIS Z0237:2000, the adhesive force at 23°C was measured by the 180° peeling method at a tensile speed of 300 mm/min.

Production Example 1 (Synthesis of Urethane Prepolymer)

In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate was added with respect to 100 parts by mass (solid content ratio) of polycarbonate diol having a weight average molecular weight of 1,000, and the hydroxyl groups of the polycarbonate diol were mixed with isophor. The equivalent ratio of the isocyanate groups of the ketone diisocyanate was 1/1, then 160 parts by mass of toluene was added, and the reaction was carried out at 80° C. with stirring in a nitrogen atmosphere for 6 hours or more until the isocyanate group concentration reached the theoretical amount.

Next, a solution obtained by diluting 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added, and the reaction was further carried out at 80° C. for 6 hours until both ends. A urethane prepolymer with a weight average molecular weight of 29,000 was obtained until the isocyanate group disappeared.

Production Example 2 (Synthesis of Acrylic Urethane Resin)

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

Then, 2.2 parts by mass of a radical initiator (manufactured by Nippon Seika Co., Ltd., product name "ABN-E") diluted with 210 parts by mass of toluene was added dropwise to the reaction vessel over 4 hours while maintaining at 105° C. (solid content ratio).

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

Production Example 3 (Preparation of Thermosetting Composition)

The following types and compounding amounts (all are "active ingredient ratios") of the components were blended, further diluted with methyl ethyl ketone, and stirred until uniform to prepare a curable composition with a solid content concentration (active ingredient concentration) of 61% by mass. solution of the substance.

Acrylic polymer: compounding amount = 26.07 parts by mass

Acrylic polymer 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 (weight average molecular weight: 40 10,000, glass transition temperature: -1°C), equivalent to the above-mentioned component (A1).

Epoxy compound (1): compounding 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) corresponds to the above-mentioned component (B1).

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

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

Epoxy compound (3): compounding amount=1.7 parts by mass

Bisphenol-A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1055", epoxy equivalent = 800 to 900 g/eq) corresponds to the above-mentioned component (B1).

Thermosetting agent: compounding amount = 0.42 parts by mass

Dicyandiamide (manufactured by ADEKA Corporation, product name "ADEKA HARDNER EH-3636AS", activated hydrogen amount=21 g/eq) corresponds to the above-mentioned component (B2).

Curing accelerator: compounding amount = 0.42 parts by mass

2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "Curazole2PHZ") corresponds to the above-mentioned component (B3).

Colorant: compounding amount = 0.20 parts by mass

Carbon black (manufactured by Mitsubishi Chemical Corporation, product name "#MA650", average particle diameter=28 nm) corresponds to the above-mentioned component (C).

Silane coupling agent: compounding amount = 0.09 parts by mass

3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM403"), molecular weight=236.64, and corresponds to the above-mentioned component (D).

·Inorganic filler: compounding amount = 55.5 parts by mass

A silica filler (manufactured by Admatechs, product name "SC2050MA", average particle diameter=0.5 μm) corresponds to the above-mentioned component (E).

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

<Adhesive resin>

Acrylic copolymer (i): Mw60 having a structural unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio) 10,000 acrylic copolymers.

Acrylic copolymer (ii): having a compound derived from n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid = 86.0/8.0/5.0/1.0 (mass The acrylic copolymer of Mw 600,000 of the structural unit of the raw material monomer than) constitutes.

<Additive>

- Isocyanate crosslinking agent (i): Tosoh Corporation make, product name "Coronate L", solid content concentration: 75 mass %.

<Thermally Expandable Particles>

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

<Release material>

Heavy release film: Lintec Co., Ltd., product name "SP-PET382150", a release agent layer formed of a silicone-based release agent is provided on one side of a polyethylene terephthalate (PET) film material, thickness: 38μm.

Light release film: Lintec Co., Ltd., product name "SP-PET381031", a material in which a release agent layer formed of a silicone-based release agent is provided on one side of a PET film, thickness: 38 μm.

Example 1

An adhesive laminate having the following configuration was produced in the following procedure: in the adhesive laminate 2b shown in FIG. 2( b ), in the second adhesive layer (X2) of the adhesive sheet (I) , and a release material is further laminated on the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film.

[1] Production of pressure-sensitive adhesive sheet (I)

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

5.0 parts by mass (solid content ratio) of the above-mentioned isocyanate-based crosslinking agent (i) was mixed with 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (i) as an adhesive resin, diluted with toluene, and stirred until uniform to prepare An adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass was obtained.

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

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

Moreover, the adhesive force of the 1st pressure-sensitive adhesive layer (X1) measured by the said method was 0.3 N/25mm.

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

0.8 parts by mass (solid content ratio) of the above-mentioned isocyanate-based crosslinking agent (i) was mixed with 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (ii) as an adhesive resin, diluted with toluene, and stirred until uniform to prepare An adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass was obtained.

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

However, the shear storage elastic modulus G' (23) at 23 degreeC of the 2nd pressure-sensitive adhesive layer (X2) was 9.0*10< ⁴ >Pa.

Moreover, the adhesive force of the 2nd pressure-sensitive adhesive layer (X2) measured by the said method was 1.0 N/25mm.

(1-3) Preparation of base material (Y)

To 100 parts by mass of solid content of the acrylic urethane-based resin obtained in Production Example 2, 6.3 parts by mass (solid content ratio) of an isocyanate-based crosslinking agent (i) and dioctylbis(2-ethyl) as a catalyst were blended 1.4 parts by mass (solid content ratio) of tin hexanoate and the above-mentioned thermally expandable particles (i) were diluted with toluene and stirred until uniform to prepare a resin composition having a solid content concentration (active ingredient concentration) of 30% by mass.

However, the content of the thermally expandable particles (i) was 20% by mass with respect to the total amount (100% by mass) of the active ingredients in the obtained resin composition.

)的表面上涂布该树脂组合物而形成涂膜，将该涂膜于100℃干燥120秒钟，形成了厚度50μm的膨胀性基材层(Y1)。Then, as a non-thermally expandable base material, a polyethylene terephthalate (PET) film with a thickness of 50 μm (manufactured by Toyobo Co., Ltd., product name “COSMOSHINE A4100”, probe tack value:

) surface was coated with the resin composition to form a coating film, and the coating film was dried at 100° C. for 120 seconds to form an intumescent base material layer (Y1) with a thickness of 50 μm.

Here, the PET film as the non-thermally expandable base material described above corresponds to the non-expandable base material layer (Y2).

The base material (Y) which consists of the intumescent base material layer (Y1) with a thickness of 50 micrometers and the non-expandable base material layer (Y2) with a thickness of 50 micrometers was produced as mentioned above.

In addition, as a sample for measuring the physical property value of the intumescent base material layer (Y1), the resin composition was applied on the surface of the release agent layer of the above-mentioned light release film to form a coating film, and the coating film was heated at 100° C. After drying for 120 seconds, an intumescent base material layer (Y1) having a thickness of 50 μm was formed in the same manner.

Then, the storage elastic modulus and probe tack value at each temperature of the intumescent base material layer (Y1) were measured based on the above-mentioned measuring method. The measurement results are as follows.

· Storage modulus E'(23) at 23°C = 2.0×10 ⁸ Pa

· Storage modulus E'(100) at 100°C = 3.0×10 ⁶ Pa

· Storage modulus E'(208) at 208°C = 5.0×10 ⁵ Pa

·Probe viscosity = 0mN/5mmφ

(1-4) Lamination of each layer

The non-expandable base material layer (Y2) of the base material (Y) produced in the above (1-3) and the second pressure-sensitive adhesive layer (X2) formed in the above (1-2) are bonded together, and at the same time The intumescent base material layer (Y1) is bonded to the first pressure-sensitive adhesive layer (X1) formed in the above (1-1).

Then, a light release film/second pressure-sensitive adhesive layer (X2)/non-expandable base material layer (Y2)/expandable base material layer (Y1)/first pressure-sensitive adhesive layer (X1)/heavy The pressure-sensitive adhesive sheet (I) obtained by peeling the film.

[2] Preparation of Sheet (II) for Forming Cured Resin Film

The solution of the curable composition prepared in Production Example 3 was applied on the peeling-treated surface of the above-mentioned light peeling film to form a coating film, and the coating film was dried at 120° C. for 2 minutes to form a thermosetting resin layer with a thickness of 25 μm ( Z), the sheet (II) for cured resin film formation which consists of a thermosetting resin layer (Z) and a light peeling film was produced.

However, the adhesive force 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 thermosetting of the thermosetting resin layer (Z) was 6.5×10 ⁹ Pa.

[3] Production of adhesive laminate

The heavy release film of the pressure-sensitive adhesive sheet (I) produced in the above [1] is removed, and the exposed first pressure-sensitive adhesive layer (X1) and the exposed thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are removed. ) was bonded to the surface to obtain an adhesive laminate.

About this adhesive laminated body, the 1st adhesive layer (X1) of the adhesive sheet (I) and the sheet for cured resin film formation ( The peeling force (F ₀ ) and (F ₁ ) when the interface P of II) is separated.

As a result, the peel force (F ₀ ) at the time of separation at the interface P before the heat treatment was 200 mN/25 mm, the separation force at the interface P after the heat treatment (F ₁ ) = 0 mN/25 mm, and the separation force (F ₁ ) ) to the peeling force (F ₀ ) [(F ₁ )/(F ₀ )] was zero.

<Measurement of peeling force (F ₀ )>

After the produced adhesive laminate was allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity), the light release film on the adhesive sheet (I) side of the adhesive laminate was removed, and the The exposed 2nd pressure-sensitive adhesive layer (X2) was affixed to a stainless steel plate (SUS304, 360 grinding|polishing).

Next, the end of the stainless steel plate to which the adhesive laminate was attached was fixed to the lower chuck of a universal tensile testing machine (manufactured by Orientec Co., Ltd., product name "TENSILON UTM-4-100").

In addition, a universal tensile tester was used so that peeling occurred at the interface P of the first pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) of the pressure-sensitive adhesive laminate and the sheet (II) for forming a cured resin film. The upper clip of the adhesive laminate fixes the sheet (II) for forming a cured resin film of the adhesive laminate.

Then, the peel force measured when peeling at the interface P at a tensile speed of 300 mm/min by the 180° peel method based on JIS Z0237:2000 in the same environment as described above was referred to as "peel force (F ₀ )".

<Measurement of peeling force (F ₁ )>

The light release film on the pressure-sensitive adhesive sheet (I) side of the produced pressure-sensitive adhesive laminate was removed, and the exposed second pressure-sensitive adhesive layer (X2) was adhered to a stainless steel plate (SUS304, No. 360 polishing).

The stainless steel plate and the adhesive laminate were heated at 240° C. for 3 minutes to expand the thermally expandable particles in the thermally expandable base material layer (Y1) of the adhesive laminate.

Then, similarly to the measurement of the above-mentioned peeling force (F ₀ ), the interface P of the first pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the sheet (II) for forming a cured resin film was subjected to the above-mentioned conditions. The peeling force measured when peeling was performed was taken as "peeling force (F ₁ )".

In addition, in the measurement of peeling force (F1 ₎ , when trying to fix the cured resin film forming sheet (II) of the adhesive laminated body with the upper clamp of the universal tensile tester, at the interface P When the sheet (II) for forming a cured resin film was completely separated and the fixation could not be achieved, the measurement was terminated, and the peel force (F ₁ ) at that time was regarded as “0 mN/25 mm”.

Example 2

A cured sealing body with a cured resin film was produced in the following procedure.

(1) Mounting of semiconductor chips

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

Then, the light release film on the side of the sheet (II) for forming a cured resin film is also removed, and on the surface of the exposed thermosetting resin layer (Z), the back surface and the surface on the opposite side to the circuit surface of each semiconductor chip are formed. Nine semiconductor chips (each chip size: 6.4 mm x 6.4 mm, chip thickness: 200 μm (#2000)) were placed in contact with each other at a necessary interval.

(2) Formation of cured sealing body

The surfaces of the nine semiconductor chips and the thermosetting resin layer (Z) in at least the peripheral portion of the semiconductor chips were covered with a thermosetting sealing resin film as a sealing material, and a vacuum heating and pressure laminator (manufactured by ROHM and HAAS) was used. "7024HP5") The sealing resin film was thermosetted, and the cured sealing body was produced.

In addition, sealing conditions are as follows.

·Preheating temperature: both the table and the diaphragm are 100℃

· Vacuum: 60 seconds

·Dynamic pressurization mode: 30 seconds

·Static pressurization mode: 10 seconds

·Sealing temperature: 180℃×60 minutes

In addition, simultaneously with this sealing resin film thermosetting, the thermosetting resin layer (Z) of the sheet (II) for cured resin film formation was hardened in the said environment, and the cured resin film was obtained.

(3) Separation at interface P

After the above-mentioned (2), a heat treatment was performed for 3 minutes at 240° C., which is the expansion initiation temperature (208° C.) or higher of the heat-expandable particles. Then, at the interface P of the cured resin film thermally cured between the first pressure-sensitive adhesive layer (X1) of the pressure-sensitive adhesive sheet (I) and the thermosetting resin layer (Z) of the cured resin film-forming sheet (II) , the separation is easily achieved at one time.

After the interface P was separated, a cured sealing body with a cured resin film was obtained.

In addition, the obtained cured sealing body with a cured resin film was cooled to room temperature (25 degreeC), but the curvature was not recognized.

Claims (15)

1. An adhesive laminate comprising:

an expandable adhesive sheet (I) having a substrate (Y) and an adhesive layer (X) and containing expandable particles in any layer, and

a cured resin film-forming sheet (II) having a thermosetting resin layer (Z),

and the thermosetting resin layer (Z) of the adhesive sheet (I) and the sheet (II) for forming a cured resin film are directly laminated together,

wherein the adhesive laminate is separated at the interface P between the adhesive sheet (I) and the cured resin film-forming sheet (II) by a treatment of swelling the swellable particles.

2. The adhesive laminate according to claim 1, wherein the expandable particles are thermally expandable particles.

3. The adhesive laminate according to claim 1 or 2, wherein the thermosetting resin layer (Z) is a layer formed from a thermosetting composition (Z) containing the polymer component (a) and the thermosetting component (B).

4. The adhesive laminate according to any one of claims 1 to 3, which has the following constitution:

the pressure-sensitive adhesive sheet (I) has a pressure-sensitive adhesive layer (X) comprising a1 st pressure-sensitive adhesive layer (X1) and a2 nd pressure-sensitive adhesive layer (X2), wherein a substrate (Y) is sandwiched between the 1 st pressure-sensitive adhesive layer (X1) and the 2 nd pressure-sensitive adhesive layer (X2), and the pressure-sensitive adhesive surface of the 1 st pressure-sensitive adhesive layer (X1) and a thermosetting resin layer (Z) are directly laminated together.

5. The adhesive laminate according to any one of claims 1 to 4, wherein the substrate (Y) has a swellable substrate layer (Y1) containing swellable particles.

6. The adhesive laminate according to claim 5, wherein the adhesive layer (X) is a non-expandable adhesive layer.

7. The adhesive laminate according to claim 5, wherein the substrate (Y) comprises an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2).

8. The adhesive laminate according to claim 7, which has the following constitution:

the 1 st pressure-sensitive adhesive layer (X1) is laminated on the surface of the expandable base material layer (Y1), and the 2 nd pressure-sensitive adhesive layer (X2) is laminated on the surface of the non-expandable base material layer (Y2).

9. The adhesive laminate according to claim 8, wherein the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2) are non-expandable adhesive layers.

10. The adhesive laminate according to any one of claims 1 to 9, wherein the cured resin film-forming sheet (II) is composed of only the thermosetting resin layer (Z).

11. The adhesive laminate according to any one of claims 1 to 10, which is used for:

an object to be sealed is placed on the surface of the sheet (II) for forming a cured resin film, the object to be sealed and the surface of the sheet (II) for forming a cured resin film in at least the peripheral portion of the object to be sealed are covered with a sealing material, and the sealing material is thermally cured to form a cured sealing body including the object to be sealed.

12. The adhesive laminate according to claim 11,

the thermosetting resin layer (Z) is also thermally cured when the sealing material is thermally cured, whereby a cured resin film can be formed,

the adhesive laminate is used for: the expandable particles are separated at the interface P by the process of expanding the expandable particles, thereby obtaining a cured sealing body with a cured resin film.

13. A method of using the adhesive laminate according to any one of claims 1 to 12, the method comprising:

an object to be sealed is placed on the surface of the sheet (II) for forming a cured resin film, the object to be sealed and the surface of the sheet (II) for forming a cured resin film in at least the peripheral portion of the object to be sealed are covered with a sealing material, and the sealing material is thermally cured to form a cured sealing body including the object to be sealed.

14. The method of using an adhesive laminate according to claim 13,

when the sealing material is cured, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, and the adhesive laminate is separated at the interface P by the treatment of expanding the expandable particles to obtain a cured sealing body with a cured resin film.

15. A method for producing a cured sealing body with a cured resin film, using the adhesive laminate according to any one of claims 1 to 12, the method comprising the following steps (i) to (iii):

step (i): a step of attaching the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate to a support and placing a sealing object on a part of the surface of the cured resin film-forming sheet (II);

step (ii): a step of forming a cured resin film by coating the object to be sealed and the surface of the cured resin film-forming sheet (II) at least in the peripheral portion of the object to be sealed with a sealing material, and thermally curing the sealing material to form a cured sealing body including the object to be sealed, and also thermally curing the thermosetting resin layer (Z);

step (iii): and a step of separating the adhesive laminate at the interface P by a treatment of expanding the expandable particles to obtain a cured sealing body with a cured resin film.

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