TWI835785B - Adhesive laminate, method of using the adhesive laminate, and method of manufacturing a cured sealing body with a cured resin film - Google Patents

Abstract

The present invention relates to an adhesive laminate, which comprises an expandable adhesive sheet (I) having a substrate (Y) and an adhesive layer (X), wherein any one of the layers contains expandable particles, and a sheet (II) for forming a curable resin film having a thermosetting resin layer (Z), wherein the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet for forming a curable resin film (II) are directly laminated to form the adhesive laminate, wherein the expandable particles are separated at an interface (P) between the adhesive sheet (I) and the sheet (II) for forming a curable resin film by a process of expanding the expandable particles.

Description

Adhesive laminate, method of using the adhesive laminate, and method of manufacturing a cured sealing body with a cured resin film

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

Adhesive sheets are not only used to fix components semi-permanently, but are also used for temporary fixing to temporarily fix the target components when building materials, interior materials, electronic parts, etc. are processed or inspected. occasion. For such adhesive sheets for temporary fixation, it is required to have both adhesion during use and peelability after use.

For example, Patent Document 1 discloses a heat-peelable adhesive sheet for temporary fixing of electronic components when they are cut, wherein a heat-expandable adhesive layer containing heat-expandable microspheres is provided on at least one side of a substrate. The heat-peelable adhesive sheet is formed by adjusting the maximum particle size of the heat-expandable microspheres relative to the thickness of the heat-expandable adhesive layer, and adjusting the center line average roughness of the surface of the heat-expandable adhesive layer before heating to less than 0.4 μm. Patent document 1 states that the heat-peelable adhesive sheet can fully ensure the bonding area with the adherend when the electronic component is cut, so that the adhesion can be prevented from poor bonding such as chip scattering. On the other hand, it is stated that after use, if the heat-expandable microspheres are expanded by heating, the contact area with the adherend can be reduced, making it easy to peel off. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent No. 3594853

[The problem that the invention wants to solve]

In the processing step using the adhesive sheet as described in Patent Document 1, the object to be processed (hereinafter also referred to as the "object to be processed") is temporarily fixed using the adhesive sheet. After the object is processed, the adhesive sheet is used to temporarily fix the object to be processed. Separate the processing objects. The above-mentioned processing may include a sealing process in which an object to be processed, such as a semiconductor wafer, is covered with a sealing material made of a curable resin, and the sealing material is cured to form a cured sealing body. Here, when the above-mentioned sealing process is performed using an adhesive sheet as described in Patent Document 1, after the hardened sealing body is formed and the adhesive sheet is heated to separate the hardened sealing body, the heat of the hardened sealing body after separation is affected. Tendency to shrink and warp. A hardened sealing body that is warped and has an uneven surface may easily cause damage such as cracking when grinding the hardened sealing body in the next step, or when the hardened sealing body is transported by a device, a mechanical arm is used to transport the hardened sealing body. Undesirable situations may easily occur.

In addition, a resin film may be further provided on one surface of the hardened seal to form a hardened seal with a resin film. To produce such a hardened seal with a resin film, it is usually necessary to attach a separately prepared resin film-forming sheet to one surface of the hardened seal to harden the resin film-forming sheet to form a resin film. In addition, as described above, since the hardened seal is prone to warping during production, the workability of attaching the resin film-forming sheet due to the warping of the hardened seal is reduced, and the adhesion between the hardened resin film and the hardened seal is reduced. In addition, the hardened seal with a resin film may further warp, which may cause various disadvantages in the next step.

An object of the present invention is to provide an adhesive laminate that can perform sealing processing by fixing a sealing object to a support, and can be easily separated from the support with a small amount of force after sealing, thereby improving productivity. To produce a cured sealing body with a cured resin film that suppresses warpage and has a flat surface. [Means used to solve problems]

The present inventors discovered that there are: an expandable adhesive sheet (I) having a base material and an adhesive layer, and including a layer containing expandable particles in either layer; and a thermosetting resin layer (Z). An adhesive laminate consisting of a sheet for forming a cured resin film (II) and an adhesive sheet (I) directly laminated with the thermosetting resin layer (Z) of the sheet for forming a cured resin film (II) can solve the above problems. subject.

That is, the present invention relates to the following [1] to [13]. [1] An adhesive laminate comprising: a substrate (Y) and an adhesive layer (X), wherein either layer contains expandable particles in the expandable adhesive sheet (I), and a sheet for forming a hardening resin film (II) having a thermosetting resin layer (Z), and the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet for forming a hardening resin film (II) are directly laminated, wherein the expandable particles are expanded to separate at the interface P between the adhesive sheet (I) and the sheet for forming a hardening resin film (II). [2] The adhesive laminate as described in [1] above, wherein the expandable particles are heat-expandable particles. [3] The adhesive laminate as described in [1] or [2] above, wherein the thermosetting resin layer (Z) is a layer formed of a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B). [4] An adhesive laminate as described in any one of [1] to [3] above, which has the following structure: The adhesive layer (X) of the adhesive sheet (I) is composed of a first adhesive layer (X1) and a second adhesive layer (X2); The substrate (Y) is sandwiched between the first adhesive layer (X1) and the second adhesive layer (X2); The adhesive surface of the first adhesive layer (X1) is directly laminated with the thermosetting resin layer (Z). [5] An adhesive laminate as described in any one of [1] to [4] above, wherein the substrate (Y) has an expandable substrate layer (Y1) containing expandable particles. [6] The adhesive laminate as described in [5] above, wherein the adhesive layer (X) is a non-expandable adhesive layer. [7] The adhesive laminate as described in [5] above, wherein the substrate (Y) has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2). [8] The adhesive laminate as described in [7] above, having a structure in which the first adhesive layer (X1) is laminated on the surface of the expandable substrate layer (Y1), and the second adhesive layer (X2) is laminated on the surface of the non-expandable substrate layer (Y2). [9] The adhesive laminate as described in [8] above, wherein the first adhesive layer (X1) and the second adhesive layer (X2) are non-expandable adhesive layers. [10] The adhesive laminate as described in any one of [1] to [9] above, wherein the sheet (II) for forming a curable resin film is composed only of a thermosetting resin layer (Z). [11] The adhesive laminate as described in any one of [1] to [10] above, which is used for placing a sealing object on the surface of the sheet (II) for forming a curable resin film, and coating the aforementioned sealing object and the aforementioned surface of the sheet (II) for forming a curable resin film at least at the peripheral portion of the sealing object with a sealing material, and thermally curing the sealing material to form a cured sealing body containing the aforementioned sealing object. [12] The adhesive laminate as described in [11] is used for When the aforementioned sealing material is thermally cured, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, By causing the aforementioned expandable particles to expand, they are separated at the interface P to obtain a cured seal with a cured resin film. [13] A method for using an adhesive laminate, which is the method for using an adhesive laminate as described in any one of [1] to [12], wherein a sealing object is placed on the surface of a sheet (II) for forming a curable resin film, the aforementioned sealing object and the aforementioned surfaces of the sheet (II) for forming a curable resin film at least at the periphery of the sealing object are coated with a sealing material, and the sealing material is thermally cured to form a cured seal containing the aforementioned sealing object. [14] A method for using an adhesive laminate as described in [13] above, wherein when the aforementioned sealing material is cured, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, and by causing the aforementioned expandable particles to expand, the particles separate at the interface P, thereby obtaining a cured sealing body with a cured resin film. [15] A method for producing a hardened seal with a hardened resin film, which is a method for producing a hardened seal with a hardened resin film using an adhesive laminate as described in any one of [1] to [12], comprising the following steps (i) to (iii); • Step (i): attaching the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate to a support, and placing a sealed object on a portion of the surface of the sheet (II) for forming the hardened resin film , ･Step (ii): The aforementioned sealing object and the aforementioned surface of the sheet (II) for forming the hardened resin film on at least the peripheral portion of the sealing object are coated with a sealing material, and the sealing material is thermally cured to form a hardened sealing body including the aforementioned sealing object, and the thermosetting resin layer (Z) is also thermally cured to form a hardened resin film, ･Step (iii): The aforementioned expandable particles are expanded to separate at the interface P to obtain a hardened sealing body with a hardened resin film. [Effect of the invention]

The adhesive laminate of the present invention can fix the sealing object to the support body to perform the sealing process, and after the sealing process, it can be easily separated from the support body with a small force. In addition, by using the adhesive laminate, it is possible to improve productivity to manufacture a hardened seal with a hardened resin film having a flat surface and suppressing warping.

In this specification, whether the target layer is a "non-expandable layer" means that after a treatment for expansion for 3 minutes, the volume change rate calculated from the following formula before and after the treatment does not reach 5% by volume. That is, this layer is judged to be a "non-expansive layer". ･Volume change rate (%) = {(volume of the aforementioned layer after treatment - volume of the aforementioned layer before treatment)/volume of the aforementioned layer before treatment} × 100 Furthermore, "processing for expansion", for example, when it is a layer containing heat-expandable particles, it suffices to perform a heat treatment for 3 minutes at the expansion starting temperature (t) of the heat-expandable particles.

In this specification, "active ingredient" refers to the ingredients contained in the composition of interest, excluding the diluent solvent. In this specification, the mass average molecular weight (Mw) is a value converted to standard polystyrene measured by gel permeation chromatography (GPC), specifically, a value measured by the method described in the embodiments. In this specification, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are the same. In this specification, the lower limit and upper limit values described in stages for the preferred numerical range (e.g., the range of content, etc.) can be combined independently. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", "preferably the lower limit value (10)" and "preferably the upper limit value (60)" can be combined to form "10 to 60".

[Characteristics of adhesive laminates] The adhesive laminate of the present invention includes a base material (Y) and an adhesive layer (X), an expandable adhesive sheet (I) containing expandable particles in any layer, and a thermosetting resin layer (Z). ) is a sheet (II) for forming a cured resin film, and has a structure in which the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film are directly laminated. The adhesive laminate of the present invention can be obtained by converting any layer of the adhesive sheet (I) into a layer containing expandable particles, and by expanding the expandable particles (hereinafter also referred to as "expansion treatment"). Separation occurs at the interface P between the adhesive sheet (I) and the cured resin film forming sheet (II).

In other words, in the adhesive laminate of the present invention, the expandable particles expand through the expansion treatment, causing unevenness on the surface of the layer containing the expandable particles, and the contact between the adhesive sheet (I) and the cured resin film forming sheet (II) Area reduced. As a result, the adhesive sheet (I) and the cured resin film forming sheet (II) can be easily separated together with a small force at the interface P.

Furthermore, the treatment for expanding the expandable particles during separation at the interface P is selected in accordance with the type of expandable particles used. For example, when using thermally expandable particles, it is appropriate to heat the particles at a temperature above the expansion starting temperature (t) of the thermally expandable particles.

Furthermore, the adhesive laminate of the present invention includes a sheet (II) for forming a cured resin film having a thermosetting resin layer (Z), and one surface of the thermosetting resin layer (Z) is in contact with the adhesive sheet (I). ) consists of direct lamination. Furthermore, a sealing object is placed on the surface side of the thermosetting resin layer (Z) opposite to the side on which the adhesive sheet (I) is laminated. The sealing object may be placed directly on the other surface of the thermosetting resin layer (Z), or may be placed through an adhesive layer provided on the other surface of the thermosetting resin layer (Z). Set.

The adhesive laminate of the present invention is preferably used for: placing a sealing object on the surface of a hardened resin film forming sheet (II), covering the aforementioned sealing object and the aforementioned surface of the hardened resin film forming sheet (II) at least at the periphery of the sealing object with a sealing material, and thermally curing the sealing material to form a hardened sealing body including the aforementioned sealing object. In addition, the adhesive laminate of the present invention is more preferably used for: when the aforementioned sealing material is thermally cured, the thermosetting resin layer (Z) is also thermally cured to form a hardened resin film, and the aforementioned expandable particles are separated at the interface P by the process of expanding them to obtain a hardened sealing body with a hardened resin film.

For example, the case where a sealing object is placed on the adhesive surface of an adhesive sheet as described in Patent Document 1, the sealing object and the adhesive surface of the peripheral portion are covered with a sealing material, and the sealing material is thermally cured to produce a hardened seal. When the sealing material is thermally cured, the sealing material has a stress that causes it to shrink, but since the 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 the hardened seal obtained by separating the support and the adhesive sheet. The hardened seal after separation has different amounts of sealing material on the surface side where the sealing object exists and on the opposite surface side, so the shrinkage stress is likely to differ. The difference in shrinkage stress is the cause of the warp generated in the hardened seal. Furthermore, from the perspective of productivity, the hardened sealing body after heating is generally separated from the support body and the adhesive sheet in a state of being heated to a certain extent. Therefore, the hardening of the sealing material also progresses after the separation, and shrinkage occurs due to natural cooling, so that the hardened sealing body is more likely to be warped.

In contrast, the adhesive laminate of the present invention includes the cured resin film-forming sheet (II) having the thermosetting resin layer (Z), thereby suppressing warpage of the cured sealing body for the following reasons. In other words, when the sealing object is placed on the surface of the cured resin film forming sheet (II), covered with a sealing material, and the sealing material is thermally cured, the thermosetting resin layer (Z) is also thermally cured at the same time. At this time, a thermosetting resin layer (Z) is provided on the surface side where the sealing object is present where the amount of the sealing material is small and the shrinkage stress caused by hardening of the sealing material is small. Therefore, the thermosetting resin layer (Z) is The shrinkage stress caused by thermal hardening of the flexible resin layer (Z) acts. As a result, it is considered that the difference in shrinkage stress between the two surfaces of the hardened sealing body can be reduced, and a hardened sealing body in which warpage is effectively suppressed can be obtained. In addition, the thermosetting resin layer (Z) that contributes to suppressing warpage of the cured sealing body can be converted into a cured resin film by thermal curing. Then, by performing the above-mentioned expansion treatment and separating at the interface P, it is considered that a cured sealing body with a cured resin film having a flat surface and suppressed warpage can be produced without going through a separate step for forming a cured resin film.

[Construction of adhesive laminate] 1 to 3 are schematic cross-sectional views of the adhesive laminate showing the composition of the adhesive laminate according to the first to third aspects of the present invention. The structure of the adhesive laminate shown in FIGS. 1 to 3 according to one aspect of the present invention will be described below. Furthermore, in the following adhesive laminates of the first to third aspects of the present invention, the adhesive layer (X) (or the second adhesive layer (X2)) attached to the support may also be used. The adhesive surface and the surface of the hardened resin film forming sheet (II) opposite to the adhesive sheet (I) are further laminated with a release material.

＜First form of adhesive laminate＞ Examples of the adhesive laminate according to the first aspect of the present invention include the adhesive laminates 1a and 1b shown in FIG. 1 . The adhesive laminates 1a and 1b include an adhesive sheet (I) having a base material (Y) and an adhesive layer (X), and a cured resin film forming sheet composed of a thermosetting resin layer (Z). (II), the base material (Y) of the adhesive sheet (I) is directly laminated to the thermosetting resin layer (Z) of the cured resin film forming sheet (II).

Incidentally, the adhesive sheet (I) included in the adhesive laminate of the present invention contains expandable particles in any layer. In the adhesive laminate according to the first aspect of the present invention, as shown in FIG. 1 , the base material (Y) has an expandable base material layer (Y1) containing expandable particles. The base material (Y) having the expandable base material layer (Y1) can be a single layer composed only of the expandable base material layer (Y1) like the adhesive laminate 1a shown in Figure 1(a) The base material may also be a base material composed of a multi-layered base material having an expanding base material layer (Y1) and a non-expanding base material layer (Y2) like the adhesive laminate 1b shown in Figure 1(b).

In the adhesive laminate 1a shown in FIG1(a), the expandable particles contained in the expandable base layer (Y1) expand by the expansion treatment, and the surface of the expandable base layer (Y1) is uneven, and the contact area with the thermosetting resin layer (Z) is reduced. On the other hand, by attaching the adhesive surface of the adhesive layer (X) to the support in a manner that is fully in close contact, even if a force that generates unevenness occurs on the surface of the adhesive layer (X) side of the expandable base layer (Y1), a repulsive force from the adhesive layer is easily generated. Therefore, it is not easy to form unevenness on the surface of the adhesive layer (X) side of the expandable base layer (Y1). As a result, the adhesive laminate 1a can be easily separated at the interface P between the base material (Y) of the adhesive sheet (I) and the sheet (II) for forming the hardened resin film with a small force. Furthermore, the adhesive layer (X) of the adhesive laminate 1a can be designed to be more easily separated at the interface P by forming the adhesive layer (X) with an adhesive composition that improves the adhesive force to the support.

Furthermore, from the perspective of suppressing the stress generated by the expandable particles from being transmitted to the adhesive layer (X), it is better to use a substrate (Y) having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), as shown in the adhesive laminate 1b of FIG. 1(b). The stress caused by the expansion of the expandable particles in the expandable substrate layer (Y1) is suppressed in the non-expandable substrate layer (Y2), and thus is hardly transmitted to the adhesive layer (X). Therefore, the adhesion of the adhesive layer (X) to the support body is almost unchanged before and after the expansion treatment, and the adhesion to the support body can be well maintained. Furthermore, it is preferred that the expandable base layer (Y1) and the thermosetting resin layer (Z) of the sheet (II) for forming the curable resin film are directly laminated, and the adhesive layer (X) is laminated on the surface of the non-expandable base layer (Y2), as in the adhesive laminate 1b shown in FIG. 1( b).

＜Second form of adhesive laminate＞ Examples of the adhesive laminate according to the second aspect of the present invention include the adhesive laminates 2a and 2b shown in FIG. 2 . The adhesive laminates 2a and 2b have the following structure: the adhesive layer (X) of the adhesive sheet (I) is composed of a first adhesive layer (X1) and a second adhesive layer (X2). The first adhesive layer (X1) and the second adhesive layer (X2) sandwich the base material (Y), and the adhesive surface of the first adhesive layer (X1) is directly laminated to the thermosetting resin layer (Z). Furthermore, in the adhesive laminate according to the second aspect of the present invention, the adhesive surface of the second adhesive layer (X2) is attached to the support.

In the second aspect of the adhesive laminate of the present invention, it is also preferred that the substrate (Y) has an expandable substrate layer (Y1) containing expandable particles. The substrate (Y) having the expandable substrate layer (Y1) may be a substrate consisting of a single layer consisting of only the expandable substrate layer (Y1), as in the adhesive laminate 2a shown in FIG2(a), or may be a substrate consisting of a multilayer structure of an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), as in the adhesive laminate 2b shown in FIG2(b).

However, as mentioned above, in order to form an adhesive laminate that can maintain the adhesion between the second adhesive layer (X2) and the support well before and after the expansion treatment, the base material (Y) is preferably expandable. The base material layer (Y1) and the non-expanding base material layer (Y2). Furthermore, in the adhesive laminate according to the second aspect of the present invention, when the base material (Y) having an expandable base material layer (Y1) and a non-expandable base material layer (Y2) is used, it is preferably as shown in the figure As shown in 2(b), there is a first adhesive layer (X1) laminated on the surface of the intumescent base material layer (Y1), and a second adhesive layer (X2) laminated on the non-intumescent base material layer. The apparent composition of (Y2).

In the adhesive laminate according to the second aspect of the present invention, the expandable particles in the expandable base material layer (Y1) constituting the base material (Y) expand through expansion treatment, and the expandable base material layer (Y1) The surface is uneven. Then, due to the unevenness produced on the surface of the expandable base material layer (Y1), the first adhesive layer (X1) also bulges, and unevenness is also formed on the adhesive surface of the first adhesive layer (X1). Therefore, the first adhesive layer The contact area between the agent layer (X1) and the thermosetting resin layer (Z) decreases. As a result, by the expansion treatment, the first adhesive layer (X1) of the adhesive sheet (I) and the cured resin film forming sheet (II) can be easily separated together with a small force at the interface P. Furthermore, in the adhesive laminate of the second aspect of the present invention, from the viewpoint of being an adhesive laminate that can be easily separated at the interface P with less force, the adhesive sheet (I) is preferred. The expandable base material layer (Y1) of the base material (Y) is directly laminated to the first adhesive layer (X1).

＜Third form of adhesive laminate＞ An example of the adhesive laminate according to the third aspect of the present invention is the adhesive laminate 3 shown in FIG. 3 . The adhesive laminate 3 shown in Figure 3 has: a first adhesive layer (X1), which is an expandable adhesive layer containing expandable particles, and is provided on one surface side of the base material (Y). The other surface side of (Y) has an adhesive sheet (I) with a non-expandable adhesive layer, that is, a second adhesive layer (X2), and the first adhesive layer (X1) and the cured resin film forming sheet ( II) The thermosetting resin layer (Z) is directly laminated. In the adhesive laminate 3, the adhesive surface of the second adhesive layer (X2) is attached to the support. Furthermore, the base material (Y) included in the adhesive laminate according to the third aspect of the present invention is preferably composed of a non-expanding base material layer.

In the adhesive laminate according to the third aspect of the present invention, through the expansion treatment, the expandable particles in the expandable adhesive layer, that is, the first adhesive layer (X1) expand to the surface of the first adhesive layer (X1). Asperity occurs, 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 adhesive layer (X1) on the base material (Y) side, unevenness is less likely to occur. Therefore, by the expansion treatment, unevenness is easily formed on the surface of the thermosetting resin layer (Z) side of the first adhesive layer (X1). As a result, the first adhesive layer (X1) of the adhesive sheet (I) The interface P with the cured resin film forming sheet (II) can be easily separated together with a small force.

[Various physical properties of adhesive laminate] The adhesive laminate of one aspect of the present invention can be easily separated at the interface P between the adhesive sheet (I) and the sheet for forming a hardened resin film (II) with a small force by means of expansion treatment. Here, in the adhesive laminate of one aspect of the present invention, after the thermosetting resin layer (Z) is thermally cured to form a cured resin film, the peeling force (F 1 ) at the time of separation at the interface P of the cured resin film formed by curing the thermosetting resin layer (Z) of the adhesive sheet ( _I ) and the cured resin film forming sheet (II) by expansion treatment is usually 0 to 2000 mN/25 mm, preferably 0 to 1000 mN/25 mm, more preferably 0 to 500 mN/25 mm, further preferably 0 to 150 mN/25 mm, further more preferably 0 to 100 mN/25 mm, further more preferably 0 to 50 mN/25 mm. The case where the peeling force (F ₁ ) is 0 mN/25 mm also includes a case where the peeling force cannot be measured because it is too small even if the peeling force is measured by the method described in the embodiment.

Furthermore, from the viewpoint of fully fixing the object to be sealed before the thermosetting resin layer (Z) is heat-cured and expanded, so as not to adversely affect the sealing operation, the adhesion between the thermosetting resin layer (Z) of the adhesive sheet (I) and the sheet (II) for forming the curing resin film is preferably high. From the above viewpoints, in the adhesive laminate of one aspect of the present invention, the peeling force (F0) at the time of separation at the interface P between the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet for forming a curing resin film ( _II ) before the thermosetting resin layer (Z) is thermally cured and before the expansion treatment is performed is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, even more preferably 160 mN/25 mm or more, and further preferably 50000 mN/25 mm or less.

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

The peeling force (F ₁ ) and the peeling force (F ₀ ) refer to the values measured by the method described in the embodiment. Furthermore, when using heat-expandable particles, the temperature condition for measuring the peeling force (F ₁ ) can be above the expansion starting temperature (t) of the heat-expandable particles. Moreover, when using heat-expandable particles, the temperature condition for measuring the peeling force (F ₀ ) can be below the expansion starting temperature (t) of the heat-expandable particles, which is basically room temperature (23° C.).

In the adhesive laminate of one embodiment of the present invention, at room temperature (23°C), the adhesive force of the adhesive layer (X) (the first adhesive layer (X1) and the second adhesive layer (X2)) of the adhesive sheet (I) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm, even more preferably 0.4 to 6.0 N/25 mm, and even more preferably 0.5 to 4.0 N/25 mm. When the adhesive sheet (I) has a first adhesive layer (X1) and a second adhesive layer (X2), the adhesion of the first adhesive layer (X1) and the second adhesive layer (X2) are preferably within the above-mentioned ranges respectively. However, from the viewpoint of improving the adhesion with the support and making it easier to separate at the interface P, it is more preferable that the adhesion between the support and the attached second adhesive layer (X2) is higher than the adhesion of the first adhesive layer (X1).

Furthermore, in the adhesive laminate according to one aspect of the present invention, from the viewpoint of achieving good adhesion to the sealing object, the surface of the cured resin film forming sheet (II) on the side on which the sealing object is placed is , preferably those with adhesive properties. Specifically, at room temperature (23°C), the adhesive force of the surface of the cured resin film forming sheet (II) on which the sealing object is placed is preferably 0.01 to 5N/25mm, more preferably 0.05 ~4N/25mm, preferably 0.1~3N/25mm. Here, when the sheet (II) for forming a cured resin film is composed of only the thermosetting resin layer (Z), the adhesive force on the surface of the thermosetting resin layer (Z) may be adjusted to the above range. Moreover, when the sheet (II) for forming a cured resin film has a thermosetting resin layer (Z) and an adhesive layer, the adhesive force of the adhesive layer may be adjusted to the above range.

In addition, in this specification, these adhesive forces mean the value measured by the method described in an Example.

The substrate (Y) of the adhesive sheet (I) is a non-adhesive substrate. In the present invention, whether it is a non-adhesive substrate is determined if the probe viscosity value of the substrate surface measured according to JIS Z0237:1991 is less than 50mN/5mmφ, then the substrate is determined to be a "non-adhesive substrate". The probe viscosity value of the surface of the substrate (Y) of the adhesive sheet (I) used in one embodiment of the present invention is usually less than 50mN/5mmφ, preferably less than 30mN/5mmφ, more preferably less than 10mN/5mmφ, and more preferably less than 5mN/5mmφ. In addition, in this specification, the probe viscosity value of the substrate surface means the value measured by the method described in the embodiment.

Each layer constituting the adhesive laminate of the present invention will be described below.

[Constitution of the adhesive sheet (I)] The adhesive sheet (I) of the adhesive laminate of the present invention has a base material (Y) and an adhesive layer (X), and is an expandable adhesive sheet containing expandable particles in either layer. When the layer containing expandable particles is included in the composition of the base material (Y), and when it is included in the composition of the adhesive layer (X), the adhesive sheet (I) used in one aspect of the present invention is Divided into the following forms. ･Adhesive sheet (I) of the first aspect: An adhesive sheet (I) having a base material (Y) having an expandable base material layer (Y1) containing expandable particles. ･Second aspect of the adhesive sheet (I): An adhesive sheet (I) having an expandable adhesive layer containing expandable particles, that is, a first adhesive layer (X1) on both sides of the base material (Y) , and the non-expanding adhesive layer is the second adhesive layer (X2).

<Adhesive sheet (I) of the first aspect> The adhesive sheet (I) of the first aspect, as shown in FIGS. 1 and 2, may include a substrate (Y) having an expandable substrate layer (Y1) containing expandable particles. In the adhesive sheet (I) of the first aspect, from the viewpoint that the interface P can be easily separated at once with a small force, the adhesive layer (X) is preferably a non-expandable adhesive layer. Specifically, in the adhesive sheet (I) of the adhesive layer composite 1a, 1b shown in FIG. 1, the adhesive layer (X) is preferably a non-expandable adhesive layer. In the adhesive sheet (I) of the adhesive laminates 2a and 2b shown in FIG. 2 , the first adhesive layer (X1) and the second adhesive layer (X2) are preferably both non-expandable adhesive layers.

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

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

Furthermore, in this specification, for example, when the adhesive sheet (I) has a plurality of adhesive layers as shown in FIG2 , the above-mentioned “thickness of adhesive layer (X)” means the thickness of each adhesive layer (in FIG2 , the thickness of each adhesive layer (X1) and (X2)). In addition, in this specification, the thickness of each layer constituting the adhesive layer assembly means the value measured by the method described in the embodiment.

In the adhesive sheet (I) of the first aspect, before the expansion treatment, the thickness ratio [(Y1)/(X)] of the expandable base material layer (Y1) and the adhesive layer (X) is preferably 1000 or less. , preferably below 200, preferably below 60, and even better still below 30. If the thickness ratio is 1000 or less, an adhesive layer can be easily separated with a small force at the interface P between the adhesive sheet (I) and the cured resin film forming sheet (II) by the expansion process. Fit. Furthermore, the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 5.0 or more.

Moreover, in the adhesive sheet (I) of the first aspect, the base material (Y) may be composed only of the expandable base material layer (Y1) as shown in Figure 1(a), or it may be as shown in Figure 1(a). As shown in 1(b), there is an expandable base material layer (Y1) on the cured resin film forming sheet (II) side, and a non-expandable base material layer (Y2) on the adhesive layer (X) side.

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

＜Second Aspect Adhesive Sheet (I)＞ The adhesive sheet (I) of the second aspect, as shown in Figure 3, has a first adhesive layer (X1) with an expandable adhesive layer containing expandable particles on both sides of the base material (Y). ), and the second adhesive layer (X2) of the non-expanding adhesive layer. Furthermore, the adhesive sheet (I) of the second aspect is the first adhesive layer (X1) of the expandable adhesive layer, and is directly connected to the thermosetting resin layer (Z) of the cured resin film forming sheet (II). get in touch with. Furthermore, in the adhesive sheet (I) of the second aspect, the base material (Y) is preferably a non-expanding base material. The non-expanding base material is preferably composed only of the non-expanding base material layer (Y2).

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

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

In the following, the expandable particles contained in any layer constituting the adhesive sheet (I) will be described, and the expandable base material layer (Y1) and the non-expandable base material layer (Y2) constituting the base material (Y) will be described in detail, and Adhesive layer (X).

<Expandable Particles> The expandable particles used in the present invention can be any particles that expand by a specific expansion treatment. The average particle size of the expandable particles used in one embodiment of the present invention before expansion at 23°C is preferably 3 to 100 μm, more preferably 4 to 70 μm, even more preferably 6 to 60 μm, and even more preferably 10 to 50 μm. Furthermore, the average particle size of the expandable particles before expansion is the volume median particle size ( _D50 ), which means the particle size with a cumulative volume frequency equivalent to 50% calculated from the smaller particle size of the expandable particles before expansion in the particle distribution of the expandable particles before expansion measured using a laser diffraction particle size distribution measuring device (e.g., manufactured by Malvern, product name "Mastersizer 3000").

The 90% particle size (D ₉₀ ) of the expandable particles before expansion at 23° C. used in one aspect of the present invention is preferably 10 to 150 μm, more preferably 20 to 100 μm, even more preferably 25 to 90 μm, and even more preferably 30 to 80 μm. The 90% particle size (D ₉₀ ) of the expandable particles before expansion refers to the particle size whose cumulative volume frequency calculated from the smaller particle size of the expandable particles before expansion is equivalent to 90% in the particle distribution of the expandable particles before expansion measured using a laser diffraction particle size distribution measuring device (e.g., Mastersizer 3000 manufactured by Malvern Corporation).

The expandable particles used in one aspect of the present invention are preferably thermally expandable particles expanded by heat treatment above the expansion starting temperature (t). The heat-expandable particles used in one aspect of the present invention may be particles that do not expand when the sealing material is hardened and have an expansion starting temperature (t) higher than the hardening temperature of the sealing material. Specifically, it is preferred. These are thermally expandable particles whose expansion starting temperature (t) is adjusted to 60 to 270°C. Furthermore, the expansion starting temperature (t) is appropriately selected depending on the hardening temperature of the sealing material used. In addition, in this specification, the expansion start temperature (t) of the heat-expandable particle means the value measured based on the following method.

(Method for determining the expansion starting temperature (t) of thermal expansion particles) In an aluminum cup with a diameter of 6.0 mm (inner diameter of 5.65 mm) and a depth of 4.8 mm, add 0.5 mg of thermal expansion particles as the test object, and cover it with an aluminum cover (diameter of 5.6 mm, thickness of 0.1 mm) to prepare a sample. Using a dynamic viscoelasticity measuring device, the height of the sample is measured in a state where a pressure of 0.01 N is applied to the sample from the upper part of the aluminum cover. Then, while a pressure of 0.01 N is applied to the sample, the temperature is heated from 20°C to 300°C at a heating rate of 10°C/min, and the displacement in the vertical direction of the pressure is measured. The displacement starting temperature in the positive direction is taken as the expansion starting temperature (t).

As the heat-expandable particles, a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an inner component that is enclosed in the outer shell and vaporizes when heated to a specific temperature is preferred. Examples of the thermoplastic resin constituting the shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, poly Vinylidene chloride, polyethylene, etc.

Examples of the components contained in the 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, cycloheptane Tridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, isotridecane, 4-methyldodecane, Isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isoctadecane, isopenadecane, 2,6,10,14-Tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane , Pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. These included ingredients can be used individually or two or more types can be used in combination. The expansion starting temperature (t) of the thermally expandable particles can be adjusted by appropriately selecting the type of encapsulated components.

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

＜Expansive base material layer (Y1)＞ The expandable base material layer (Y1) of the adhesive sheet (I) used in one aspect of the present invention contains expandable particles and can be expanded by a specific expansion treatment. The content of the expandable particles in the expandable base material layer (Y1) is preferably 1 to 40 mass%, more preferably 5, relative to the total mass (100 mass%) of the expandable base material layer (Y1). ~35% by mass, more preferably 10-30% by mass, and still more preferably 15-25% by mass.

Furthermore, from the viewpoint of improving the interlayer adhesion between the expandable substrate layer (Y1) and other laminated layers, the surface of the expandable substrate layer (Y1) may be subjected to surface treatment such as oxidation or embossing, easy-to-attach treatment, or primer treatment. Oxidation methods include, for example, corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, and embossing methods include, for example, sandblasting and solvent treatment.

In one aspect of the present invention, the expandable substrate layer (Y1) is preferably a heat expandable substrate layer containing heat expandable particles, and more preferably the heat expandable substrate layer satisfies the following requirement (1). Requirement (1): At the expansion starting temperature (t) of the heat expandable particles, the storage modulus E'(t) of the heat expandable substrate layer is 1.0×10 ⁷ Pa or less. In this specification, the storage modulus E' of the heat expandable substrate layer at a specific temperature means a value measured by the method described in the embodiment.

The above requirement (1) can be said to be an index showing the rigidity of the heat-expandable base layer before the heat-expandable particles expand. In order to easily separate the adhesive sheet (I) and the sheet for forming the curing resin film (II) with a small force at the interface P, it is necessary to easily form irregularities on the surface of the adhesive sheet (I) on the side laminated with the thermosetting resin layer (Z) when heated to a temperature above the expansion starting temperature (t). In other words, in the heat-expandable base layer satisfying the above requirement (1), the heat-expandable particles expand and become sufficiently large at the expansion starting temperature (t), and irregularities are easily formed on the surface of the adhesive sheet (I) on the side laminated with the thermosetting resin layer (Z). As a result, an adhesive laminate can be formed which can be easily separated with a small force at the interface P between the adhesive sheet (I) and the sheet for forming a hardened resin film (II).

From the above point of view, the storage modulus E'(t) of the thermally expandable base material layer specified in requirement (1) is preferably 9.0×10 ⁶ Pa or less, more preferably 8.0×10 ⁶ Pa or less, and more preferably Preferably it is 6.0×10 ⁶ Pa or less, further preferably 4.0×10 ⁶ Pa or less, still more preferably 1.0×10 ⁶ Pa or less. In addition, by suppressing the flow of the expanded thermally expandable particles and improving the shape maintainability of the unevenness formed on the surface of the adhesive sheet (I) on the side where the thermosetting resin layer (Z) is laminated, it is possible to maintain the shape of the surface at the interface P with a little From the perspective of easier separation due to force, the storage modulus E'(t) of the thermally expandable base material layer specified in requirement (1) is preferably 1.0×10 ³ Pa or more, more preferably 1.0×10 ⁴ Pa or more. More preferably, it is 1.0×10 ⁵ Pa or more.

The expandable base material layer (Y1) is preferably formed of a resin composition (y) containing resin and expandable particles. Furthermore, the resin composition (y) may contain additives for base materials as necessary within a range that does not impair the effects of the present invention. Examples of additives for base materials include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, anti-adhesive agents, colorants, and the like. In addition, these additives for base materials may be used individually, or two or more types may be used in combination. 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.

The expandable particles contained in the resin composition (y) that forms the expandable base material layer (Y1) are preferably thermally expandable particles as described above. The content of the expandable particles is preferably 1 to 40 mass %, more preferably 5 to 35 mass %, and still more preferably 10 mass % with respect to the total amount of active ingredients (100 mass %) of the resin composition (y). ~30 mass%, and more preferably 15-25 mass%.

The resin contained in the resin composition (y) of the forming material of the expandable base material layer (Y1) may be a non-adhesive resin or an adhesive resin. In other words, even if the resin contained in the resin composition (y) is an adhesive resin, as long as the adhesive resin and the polymerizable compound are in contact with each other during the formation of the expandable base material layer (Y1) from the resin composition (y). After the polymerization reaction, the obtained resin becomes a non-adhesive resin, and the expandable base material layer (Y1) containing the resin becomes non-adhesive.

The mass 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 constituent units, the morphology of the copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.

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

Furthermore, from the viewpoint of forming an expandable base material layer (Y1) that satisfies the above requirement (1), the resin contained in the resin composition (y) preferably contains an acrylic urethane resin and an olefin. One or more types selected from resins. Moreover, the above-mentioned acrylic urethane resin is preferably the following resin (U1). ･Acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing (meth)acrylate.

(Acrylic urethane resin (U1)) Examples of the urethane prepolymer (UP) of the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyisocyanate. Furthermore, the urethane prepolymer (UP) is preferably obtained by further carrying out a chain extension reaction using a chain extender.

Polyols used as raw materials for urethane prepolymers (UP) include, for example, alkylene polyols, ether polyols, ester polyols, esteramide polyols, and ester/ether polyols. Alcohols, carbonate polyols, etc. These polyhydric alcohols can be used individually or in combination of 2 or more types. The polyol used in one aspect of the present invention is preferably a diol; more preferably, it is an ester type glycol, an alkylene type glycol and a carbonate type glycol; and more preferably, it is an ester type glycol or a carbonate type glycol. diol.

Examples of ester glycols include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol One or two or more glycols selected from alcohols, propylene glycol, diethylene glycol, dipropylene glycol, and alkylene glycols, etc., together with phthalic acid, isophthalic acid, terephthalic acid, and naphthalene diol. Carboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chlorobridge acid, maleic acid , fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydro-p- A condensation polymer of one or more selected from dicarboxylic acids such as phthalic acid and methylhexahydrophthalic acid and their acid anhydrides. Specific examples include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, and polyhexamethylene isophthalate diol. , polyneopentyl adipate glycol, polyethylene propylene adipate glycol, polyethylene butylene adipate glycol, polybutylene hexamethylene adipate glycol, Polyethylene adipate glycol, poly(tetramethylene ether) adipate glycol, poly(3-methylpentane adipate) glycol, polyethylene azelate Glycol, polyethylene sebacate glycol, polybutylene azelaate glycol, polybutylene sebacate glycol and polyneopentyl terephthalate glycol, etc.

Alkylene glycols include, for example, alkylene glycols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; Alcohol etc.

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

Polyisocyanates used as raw materials of urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, etc. These polyisocyanates may be used alone or in combination of two or more. In addition, these polyisocyanates may be trihydroxymethylpropane adduct type modified bodies, biuret type modified bodies obtained by reaction with water, and isocyanurate type modified bodies containing isocyanurate rings.

Among these, the polyvalent isocyanate used in one aspect of the present invention is particularly preferably diisocyanate, and more preferably 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate ( 1 or more types selected from 2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate.

Examples of alicyclic diisocyanates include 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, and 1,3 - Cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., preferably isophorone Diisocyanate (IPDI).

In one aspect of the present invention, the urethane prepolymer (UP) as the main chain of the acrylic urethane resin (U1) is a reactant of diol and diisocyanate, preferably two Linear urethane prepolymer with ethylenically unsaturated terminal groups. A method for introducing ethylenically unsaturated groups into both terminals of the linear urethane prepolymer includes reacting a diol with a diisocyanate compound and then reacting the resulting linear urethane prepolymer. A method of reacting the terminal NCO group with hydroxyalkyl (meth)acrylate.

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

The vinyl compound as the side chain of the acrylic urethane resin (U1) contains at least (meth)acrylate. The (meth)acrylate is preferably one or more selected from (meth)acrylate alkyl esters and (meth)acrylate hydroxyalkyl esters; more preferably, a combination of (meth)acrylate alkyl esters and (meth)acrylate hydroxyalkyl esters is used.

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

The carbon number of the alkyl group of the (meth)acrylate is preferably 1-24, more preferably 1-12, even more preferably 1-8, and even more preferably 1-3.

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

Examples of vinyl compounds other than (meth)acrylates include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methyl vinyl ether, ethyl vinyl ether, etc. Vinyl ethers; vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, methyl (Acrylamide) and other polar group-containing monomers. These can be used individually or two or more types can be used in combination.

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

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

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

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

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 but less than 910 kg/m ^{3 )} . 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 low density Polyethylene resin such as polyethylene; polypropylene resin (PP); polybutylene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly(4-methyl-1-pentene) ( PMP); ethylene-vinyl acetate copolymer (EVA); ethylene-vinyl alcohol copolymer (EVOH); ethylene-propylene-(5-ethylene-2-norbornene) and other olefin terpolymers, etc. .

In one aspect of the present invention, the olefinic resin may be a modified olefinic resin that has been further modified by one or more of acid modification, hydroxy modification, and acrylic modification.

For example, the acid-modified olefin resin obtained by acid-modifying an olefin resin includes a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or anhydride thereof with the above-mentioned unmodified olefin resin. Examples of the unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, and maleic acid. Lenic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc. In addition, unsaturated carboxylic acid or its anhydride may be used individually or in combination of 2 or more types.

Acrylic acid-modified olefin resins obtained by subjecting olefin resins to acrylic modification include olefin resins without modification of the main chain as mentioned above and graft-polymerized with (meth)acrylic acid alkyl esters as side chains. Modified polymers. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1 to 20, more preferably 1 to 16, and still more preferably 1 to 12. Examples of the above-mentioned (meth)acrylic acid alkyl ester include the same compounds that can be selected as the monomer (a1') described below.

The hydroxy-modified olefinic resin obtained by subjecting the olefinic resin to hydroxyl modification can be exemplified by the modified polymer obtained by grafting a hydroxyl-containing compound with the above-mentioned unmodified olefinic resin in the main chain. The above-mentioned hydroxyl-containing compound can be exemplified by hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; unsaturated alcohols such as vinyl alcohol and allyl alcohol, etc.

(Resins other than acrylic urethane resin and olefin resin) In one aspect of the present invention, the resin composition (y) may contain resins other than acrylic urethane resins and olefin resins 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 naphthalate. Polyester resins such as diesters; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane resins not equivalent to acrylic urethane resins Acid ester; polystyrene; polyetheretherketone; polyetherstyrene; polyphenylene sulfide; polyetherimide, polyimide and other polyimide resins; polyamide resin; acrylic resin; fluorine series Resin etc.

However, from the viewpoint of forming the expandable base material layer (Y1) that satisfies the above requirement (1), the content ratio of resins other than acrylic urethane resin and olefin resin in the resin composition (y) is Less is better. The content ratio of resins other than acrylic urethane resin and olefin resin is preferably less than 30 parts by mass and more than 100 parts by mass of the total resin contained in the resin composition (y). Preferably it is less than 20 parts by mass, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, still more preferably less than 1 part by mass.

(Solvent-free resin composition (y1)) Examples of the resin composition (y) used in one aspect of the present invention include an oligomer having an ethylenically unsaturated group with a mass average molecular weight (Mw) of 50,000 or less, an energy-beam polymerizable monomer, and the above-mentioned expandable particles. A solvent-free resin composition (y1) formed by blending without solvent. In the solvent-free resin composition (y1), no solvent is blended, but the energy ray polymerizable monomer contributes to improving the plasticity of the oligomer. By irradiating the coating film formed of the solvent-free resin composition (y1) with energy rays, the expandable base material layer (Y1) that satisfies the above requirement (1) can be easily formed.

The type, shape, and blending amount (content) of the expandable particles blended in the solvent-free resin composition (y1) are as described above.

The mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and still more preferably 3,000 to 35,000. , and even better is 4,000 to 30,000.

Moreover, the aforementioned oligomer may be any one having an ethylenically unsaturated group with a mass average molecular weight of 50,000 or less among the resins contained in the aforementioned resin composition (y), and is preferably the aforementioned urethane. Prepolymer (UP). Furthermore, a modified olefin-based resin having an ethylenically unsaturated group can also be used as the oligomer.

In the solvent-free resin composition (y1), the total content of the aforementioned oligomers and energy ray polymerizable monomers is preferably: 50 to 99 mass%, more preferably 60 to 95 mass%, still more preferably 65 to 90 mass%, still more preferably 70 to 85 mass%.

Examples of the energy ray polymerizable monomer include isocamphenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentenoxy (meth)acrylate. Alicyclic polymerizable compounds such as ester, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl acrylate, etc.; phenylhydroxypropyl acrylate, benzyl acrylate, phenol ethylene oxide Aromatic polymerizable compounds such as modified acrylates; heterocyclic polymerizable compounds such as tetrahydrofuran methyl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, etc. wait. These energy ray polymerizable monomers may be used individually or in combination of two or more types.

The blending ratio of the aforementioned oligomer to the energy ray polymerizable monomer (the aforementioned 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 aspect of the present invention, the solvent-free resin composition (y1) is preferably further blended with a photopolymerization initiator. By containing a photopolymerization initiator, the curing reaction can fully proceed even when irradiated with energy rays of relatively low energy.

Examples of photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl phenyl Sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, biacetyl, 8-chloroanthraquinone, etc. These photopolymerization initiators may be used individually or in combination of two or more types.

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

<Non-expandable substrate layer (Y2)> The material forming the non-expandable substrate layer (Y2) constituting the substrate (Y) may be, for example, paper, resin, metal, etc., and may be appropriately selected according to the purpose of the adhesive laminate of one aspect of the present invention.

Examples of paper materials include thin paper, medium-grade paper, high-grade paper, impregnated paper, coated paper, copperplate paper, sulfate paper, glass paper, etc. Examples of resins include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane resins such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfone; polyetheretherketone; polyethersulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; fluorine resins, etc. Examples of metals include aluminum, tin, chromium, and titanium.

These forming materials may be composed of one type or two or more types may be used in combination. The non-expandable base material layer (Y2) using two or more forming materials in combination may include a method of laminating a paper material with a thermoplastic resin such as polyethylene, or a method of forming a metal film on the surface of a resin film or sheet containing a resin. Furthermore, the method of forming the metal layer may include, for example, a method of evaporating the above metal by a PVD method such as vacuum evaporation, sputtering, or ion plating, or a method of attaching a metal foil composed of the above metal using a general adhesive.

Furthermore, from the perspective of improving the interlayer adhesion between the non-expandable substrate layer (Y2) and other layers laminated thereon, when the non-expandable substrate layer (Y2) contains a resin, the surface of the non-expandable substrate layer (Y2) can also be subjected to surface treatment, easy-to-attach treatment, or primer treatment by oxidation or embossing in the same manner as the above-mentioned expandable substrate layer (Y1).

Moreover, when the non-expanding base material layer (Y2) contains a resin, it may also contain the said additive for base materials which may be contained in the resin composition (y) together with this resin.

The non-expandable base layer (Y2) is a non-expandable layer determined based on the above method. Therefore, the volume change rate (%) of the non-expandable base layer (Y2) calculated by the above formula is less than 5 volume%, preferably less than 2 volume%, more preferably less than 1 volume%, still more preferably less than 0.1 volume%, and still more preferably less than 0.01 volume%.

Furthermore, the non-expandable base layer (Y2) may also contain expandable particles as long as the volume change rate is within the above range. For example, by selecting the resin contained in the non-expandable base layer (Y2), the volume change rate can be adjusted to the above range even if expandable particles are contained. However, the content of expandable particles in the non-expandable base layer (Y2) is preferably less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass, relative to the total mass (100% by mass) of the non-expandable base layer (Y2).

＜Adhesive layer (X)＞ The adhesive layer (X) of the adhesive sheet (I) used in one aspect of the present invention can be formed from an adhesive composition (x) containing an adhesive resin. In addition, the adhesive composition (x) may also contain additives for adhesives such as a cross-linking agent, a tackifier, a polymerizable compound, a polymerization initiator, etc., if necessary. Each component contained in the adhesive composition (x) will be described below. Furthermore, when the adhesive sheet (I) has the first adhesive layer (X1) and the second adhesive layer (X2), the first adhesive layer (X1) and the second adhesive layer (X2) are also It can be formed from the adhesive composition (x) containing each component shown below.

(adhesive resin) The adhesive resin used in one aspect of the present invention may be a polymer that has adhesive properties alone and has a mass average molecular weight (Mw) of 10,000 or more. The mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1.5 million, and still more preferably 30,000 from the viewpoint of improving the adhesive force. ~1 million.

Specific adhesive resins include, for example, acrylic resins, urethane resins, rubber-based resins such as polyisobutylene-based resins, polyester-based resins, olefin-based resins, polysiloxane-based resins, and polyvinyl ether-based resins. Resin etc. These adhesive resins can be used alone or two or more types can be used in combination. In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited and can be any of block copolymers, random copolymers, and graft copolymers. Both are available.

The adhesive resin used in one embodiment of the present invention may also be an energy-ray-curable adhesive resin having a polymerizable functional group introduced into the side chain of the above-mentioned adhesive resin. By forming an adhesive layer with a composition containing an energy-ray-curable adhesive resin, the adhesive force can be reduced by irradiating energy rays. The polymerizable functional group may include (meth)acryl, vinyl, etc. In addition, the energy ray may include ultraviolet rays or electron beams, preferably ultraviolet rays. Furthermore, the material for forming the adhesive layer that can reduce the adhesive force by irradiating energy rays may also be a composition containing a monomer or oligomer having a polymerizable functional group. In such a composition, it is preferred to further contain a photopolymerization initiator.

In one aspect of the present invention, from the viewpoint of exhibiting excellent adhesive force, the adhesive resin preferably contains an acrylic resin. Furthermore, when the adhesive sheet (I) having the first adhesive layer (X1) and the second adhesive layer (X2) is used, the first adhesive layer (I) in contact with the cured resin film forming sheet (II) X1) contains acrylic resin, which can easily form unevenness on the surface of the first adhesive layer.

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

The content of the adhesive resin is preferably 35 to 100% by mass relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x) or the total mass (100% by mass) of the adhesive layer (X) %, 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 the present invention, when the adhesive composition (x) contains an adhesive resin having a functional group, it is preferred to further contain a crosslinking agent. The crosslinking agent is a substance that reacts with the adhesive resin having a functional group and crosslinks the adhesive resins with each other using the functional group as a crosslinking starting point.

Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, and metal chelate crosslinking agents. These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, isocyanate crosslinking agents are particularly preferred from the perspectives of increasing cohesion and adhesion, and from the perspectives of ease of obtaining.

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

(Tackifier) In one aspect of the present invention, from the viewpoint of further improving the adhesive force, the adhesive composition (x) may further contain a tackifier. In this specification, "tackifier" refers to a component that assists in improving the adhesive force of the above-mentioned adhesive resin, and is an oligomer with a mass average molecular weight (Mw) of less than 10,000, which is different from the above-mentioned adhesive resin. By. The mass average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and still more preferably 800 to 5,000.

Examples of the tackifier include rosin resins, terpene resins, styrene resins, C5 petroleum resins obtained by copolymerizing C5 distillates of pentene, isoprene, piperine, 1,3-pentadiene, etc. generated by thermal decomposition of petroleum naphtha, C9 petroleum resins obtained by copolymerizing C9 distillates of indene, vinyltoluene, etc. generated by thermal decomposition of petroleum naphtha, and hydrogenated resins obtained by hydrogenating these resins.

The softening point of the thickener is preferably 60 to 170°C, more preferably 65 to 160°C, and even more preferably 70 to 150°C. In this specification, the "softening point" of the thickener means the value measured according to JIS K 2531. The thickener may be used alone or in combination of two or more thickeners having different softening points or structures. In addition, when two or more thickeners are used, the weighted average of the softening points of the plurality of thickeners is preferably within the above range.

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

(Photopolymerization initiator) In one embodiment of the present invention, when the adhesive composition (x) is an energy-ray-curable composition and contains an energy-ray-curable adhesive resin, or a monomer or oligomer having a polymerizable functional group, the composition preferably further contains a photopolymerization initiator. By containing a photopolymerization initiator, the curing reaction can be fully carried out even by irradiation with energy rays of relatively low energy. In addition, the photopolymerization initiator can be the same as that mixed in the above-mentioned solvent-free resin composition (y1).

The content of the photopolymerization initiator is preferably 0.01 to 10 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. Preferably, it is 0.03-5 parts by mass, and more preferably, it is 0.05-2 parts by mass.

(Additives for adhesives) In one aspect of the present invention, the adhesive composition (x) may contain, in addition to the above-mentioned additives, adhesive additives used in general adhesives within the scope 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. Furthermore, these additives for adhesives may be used individually, or two or more types may be used in combination.

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

Furthermore, when the adhesive sheet (I) of the second embodiment having the expandable adhesive layer, i.e., the first adhesive layer (X1), is used, the forming material of the expandable adhesive layer, i.e., the first adhesive layer (X1), is formed by the expandable adhesive composition (x11) further containing expandable particles in the above-mentioned adhesive composition (x). The expandable particles are as described above. The content of the expandable particles is preferably 1 to 70 mass %, more preferably 2 to 60 mass %, further preferably 3 to 50 mass %, and further preferably 5 to 40 mass % relative to the total mass (100 mass %) of the active ingredients of the expandable adhesive composition (x11) or the total mass (100 mass %) of the expandable adhesive layer.

On the other hand, when the adhesive layer (X) is a non-expanding adhesive layer, the content of the expanding particles in the adhesive composition, which is the material forming the non-expanding adhesive layer, is preferably as small as possible. The content of the expanding particles in the adhesive composition (x), which is the material forming the non-expanding adhesive layer, is relative to the total amount (100 mass%) of the active ingredients of the adhesive composition (x) or the adhesive layer (X) ) of the total mass (100 mass%), preferably less than 1 mass%, more preferably less than 0.1 mass%, still more preferably less than 0.01 mass%, still more preferably less than 0.001 mass% .

Furthermore, like the adhesive laminates 2a and 2b shown in Figure 2, an adhesive sheet (I) having a first adhesive layer (X1) and a second adhesive layer (X2) of a non-expanding adhesive layer is used. At 23°C, the shear storage modulus G'(23) of the first adhesive layer (X1) of the non-expanding adhesive layer is preferably 1.0×10 ⁸ Pa or less, and more preferably 5.0×10 ⁷ Pa or less, more preferably 1.0×10 ⁷ Pa or less. If the shear storage modulus G'(23) of the first adhesive layer (X1) of the non-expanding adhesive layer is 1.0×10 ⁸ Pa or less, for example, the adhesive laminate 2a as shown in Figure 2 will be formed. In the configuration of 2b, the expansion of the expandable particles in the expandable base material layer (Y1) caused by the expansion process is easy to cause the first adhesive layer (X1) in contact with the cured resin film forming sheet (II) The surface is uneven. As a result, it is possible to obtain an adhesive laminate that can be easily separated together with a small force at the interface P between the adhesive sheet (I) and the cured resin film forming sheet (II). Furthermore, at 23°C, the shear storage modulus G' (23) of the first adhesive layer (X1) of the non-expanding adhesive layer is preferably 1.0×10 ⁴ Pa or more, and more preferably 5.0× 10 ⁴ Pa or more, more preferably 1.0×10 ⁵ Pa or more.

[Constitution of the sheet (II) for forming a hardened resin film] The sheet (II) for forming a hardened resin film of the adhesive laminate of the present invention has a thermosetting resin layer (Z). The sheet (II) for forming a hardened resin film used in one embodiment of the present invention may be a single-layer structure consisting of only a thermosetting resin layer (Z), or may be a multi-layer structure in which other layers are provided on one surface side of the thermosetting resin layer (Z). However, in the sheet (II) for forming a curable resin film used in one embodiment of the present invention, other layers may be provided on one surface side of the thermosetting resin layer (Z), but no other layers are provided on the other surface side of the thermosetting resin layer (Z), and the thermosetting resin layer (Z) is directly laminated with the adhesive sheet (I).

Here, in the sheet (II) for forming a hardened resin film used in one aspect of the present invention, an adhesive layer may be further provided on the surface side of one side of the thermosetting resin layer (Z), and a non-thermosetting substrate layer may be provided between the thermosetting resin layer (Z) and the aforementioned adhesive layer. The aforementioned adhesive layer may be formed by an adhesive composition (x) of the forming material of the aforementioned adhesive layer (X). Furthermore, the aforementioned non-thermosetting substrate layer may also be formed by the same forming material as the aforementioned non-expanding substrate layer (Y2). The following describes the thermosetting resin layer (Z) provided by the sheet (II) for forming a hardened resin film.

<Thermosetting resin layer (Z)> Thermosetting resin layer (Z) may be formed of a composition that can be heat-cured to form a curable resin film. From the viewpoint of being able to produce an adhesive laminated body having a curable resin film with a flat surface and suppressing warping, it is preferably a layer formed of a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B). In addition, the thermosetting composition (z) may further contain one or more selected from a coloring agent (C), a coupling agent (D), and an inorganic filler (E). From the above viewpoint, it is preferred to contain at least an inorganic filler (E).

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

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

Hereinafter, various components contained in the thermosetting composition (z) which is a material for forming 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 mass average molecular weight of 20,000 or more and having at least one repeating unit. By containing the polymerizable component (A) in the formed thermosetting resin layer (Z), flexibility and film-forming properties can be imparted to the thermosetting resin layer (Z), so that the sheet property maintenance property becomes good. The mass average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, more preferably 50,000 to 2,000,000, more preferably 100,000 to 1,500,000, and more preferably 200,000 to 1,000,000.

The content of component (A) is preferably: 5 to 50 mass %, more preferably 8 to 40 mass %, further preferably 10 to 30 mass %.

The polymer component (A) includes, for example, acrylic polymers, polyesters, phenoxy resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber polymers, etc. These polymer components (A) can be used alone or in combination of two or more. In addition, in this specification, acrylic polymers having epoxy groups or phenoxy resins having epoxy groups are thermosetting, and as long as they have a mass average molecular weight of 20,000 or more and have at least one type of repeating unit, they are included in the concept of polymer component (A).

Among these, the polymer component (A) is preferably one containing an acrylic polymer (A1). The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100% by mass, more preferably 70% with respect to the total amount of the polymer component (A) (100% by mass) ~100% by mass, more preferably 80-100% by mass, and still more preferably 90-100% by mass.

(Acrylic polymer (A1)) The mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably 20,000 to 3,000,000, more preferably 100,000 to 1,500,000, more preferably 150,000 to 1,200,000, and even more preferably 250,000 to 1,000,000, from the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer (Z).

The glass transition temperature (Tg) of the acrylic polymer (A1) is used to impart good adhesion to the surface of the thermosetting resin layer (Z) and to improve the cured resin film produced using an adhesive laminate. From the viewpoint of the reliability of the hardened sealing body, -60 to 50°C is preferred, -50 to 30°C is more preferred, -40 to 10°C is more preferred, and -35 to 5°C is still more preferred.

Examples of the acrylic polymer (A1) include polymers containing (meth)acrylic acid alkyl esters as the main component. Specifically, those containing (meth)acrylic acid alkyl esters having an alkyl group having 1 to 18 carbon atoms are preferred. An acrylic polymer derived from the structural unit (a1) of the ester (a1') (hereinafter also referred to as "monomer (a1')"); more preferably, it contains the structural unit (a1) and the monomer (a2) containing a functional group ') (hereinafter also referred to as "monomer (a2')") is an acrylic copolymer of the structural unit (a2). The acrylic polymer (A1) can be used alone or in combination of two or more types. In addition, when the acrylic polymer (A1) is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

The carbon number of the alkyl group of the monomer (a1') is preferably 1 to 18, more preferably 1 to 12, from the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer (Z). More preferably, it is 1-8. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group. These monomers (a1') may be used individually or in combination of two or more types.

From the viewpoint of improving the reliability of the cured sealing body with a cured resin film produced using an adhesive laminate, the monomer (a1') preferably contains a (meth)acrylic acid alkyl group having an alkyl group having 1 to 3 carbon atoms. ester, preferably methyl (meth)acrylate. From the above point of view, the content of the structural unit (a11) derived from the alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms is relative to the total structural units (100% by mass) of the acrylic polymer (A1). In other words, it is preferably 1 to 80 mass%, more preferably 5 to 80 mass%, and still more preferably 10 to 80 mass%.

Furthermore, from the viewpoint of increasing the gloss value of the cured resin film formed by thermally curing the thermosetting resin layer (Z) and improving the laser marking suitability, the monomer (a1') preferably contains an alkyl (meth)acrylate having an alkyl group with 4 or more carbon atoms, more preferably an alkyl (meth)acrylate having an alkyl group with 4 to 6 carbon atoms, and even more preferably butyl (meth)acrylate. From the above viewpoint, the content of the constituent unit (a12) derived from an alkyl (meth)acrylate having an alkyl group with 4 or more carbon atoms (preferably 4 to 6, and even more preferably 4) is preferably 1 to 70 mass%, more preferably 5 to 65 mass%, and even more preferably 10 to 60 mass% relative to the total constituent units (100 mass%) of the acrylic polymer (A1).

The content of the structural unit (a1) is preferably 50 mass% or more, more preferably 50 to 99 mass%, and still more preferably 50 mass% or more, based on all the structural units (100 mass%) of the acrylic polymer (A1). 55 to 90 mass%, more preferably 60 to 90 mass%.

The monomer (a2') is preferably one or more selected from monomers containing a hydroxyl group and monomers containing an epoxy group. Furthermore, the monomer (a2') may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing monomer include the same compounds as the above-mentioned hydroxyl group-containing compounds, preferably hydroxyalkyl (meth)acrylate, more preferably 2-hydroxyethyl (meth)acrylate.

Examples of monomers containing epoxy groups include (meth)acrylate glycidyl (meth)acrylate, (meth)acrylate β-methyl glycidyl (meth)acrylate, (meth)acrylate (3,4-epoxycyclohexyl)methyl (meth)acrylate, (meth)acrylate 3-epoxycyclo-2-hydroxypropyl, etc.; crotonate glycidyl, allyl glycidyl ether, etc. Among these monomers containing epoxy groups, (meth)acrylate containing epoxy groups is preferred, and (meth)acrylate glycidyl is more preferred.

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

Furthermore, the acrylic polymer (A1) may have structural units derived from other monomers other than the above-mentioned structural units (a1) and (a2) within a range that does not impair the effects of the present invention. Examples of other monomers include vinyl acetate, styrene, ethylene, α-olefin, and the like.

<Thermosetting component (B)> Thermosetting component (B) plays a role in thermally curing the thermosetting resin layer (Z) to form a hard curing resin film, and is a compound having a mass average molecular weight of less than 20,000. The mass average molecular weight (Mw) of the curing component (B) is preferably 10,000 or less, and more preferably 100 to 10,000.

The thermosetting component (B) is an adhesive laminate that can suppress warpage and produce a cured sealing body with a cured resin film that has a flat surface. It is preferable to include an epoxy compound having an epoxy group. (B1) and a thermal hardener (B2), preferably contain an epoxy compound (B1) and a thermal hardener (B2), and further contain a hardening accelerator (B3).

Examples of epoxy compounds (B1) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and its hydrogenated product, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phenylene skeleton epoxy resin, etc., which have two or more functional groups in the molecule and have a mass average molecular weight of less than 20,000. Epoxy compounds (B1) may be used alone or in combination of two or more.

The content of the epoxy compound (B1) is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, further preferably 10 to 150 parts by mass, and further preferably 20 to 120 parts by mass relative to 100 parts by mass of the polymer component (A), from the viewpoint of producing an adhesive laminate having a hardened sealant with a hardened resin film having a flat surface and suppressed warping.

The thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1). As the thermosetting agent, a compound having two or more functional groups that can react with the epoxy group in one molecule is preferred. The functional group may be phenolic hydroxyl, alcoholic hydroxyl, amine, carboxyl, and acid anhydride. Among these, phenolic hydroxyl, amine, or acid anhydride is preferred from the viewpoint of being able to produce an adhesive laminate of a curable sealant with a curing resin film having a flat surface and suppressing warping; phenolic hydroxyl or amine is more preferred; and amine is still more preferred.

Examples of phenol-based thermosetting agents having a phenol group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, xylok-type phenol resins, and aralkyl phenols. Resin etc. Examples of the amine-based thermosetting agent having an amine group include dicyandiamine (DICY). These thermal hardeners (B2) can be used alone or two or more types can be used in combination.

The content of the thermosetting agent (B2) is based on 100 parts by mass of the epoxy compound (B1) from the viewpoint of producing an adhesive laminate that suppresses warpage and has a flat surface of a cured sealing body with a cured resin film. In other words, it is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass.

The curing accelerator (B3) is a compound that has the function of increasing the speed of thermal curing when the thermosetting resin layer (Z) is thermally cured. Examples of the hardening accelerator (B3) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and ginseng(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, etc.; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, etc. Phenylboron salt, etc. These hardening accelerators (B13) can be used alone or two or more types can be used in combination.

The content of the hardening accelerator (B3) is higher than that of the epoxy compound (B1) and the thermosetting agent from the viewpoint of producing an adhesive laminate that suppresses warpage and has a flat surface of a hardened sealing body with a hardened resin film. The total amount of (B2) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and still more preferably 0.3 to 4 parts by mass based on 100 parts by mass.

＜Color(C)＞ The thermosetting composition (z) used in one aspect of the present invention may further contain a colorant (C). When the thermosetting resin layer (Z) formed of the thermosetting composition (z) containing the colorant (C) is thermally cured to become a cured resin film, the cured resin film can shield the surrounding device from the surrounding device. The infrared rays generated prevent malfunction of sealed objects (semiconductor chips, etc.).

The coloring agent (C) may be an organic or inorganic pigment or dye. As the dye, any dye such as acid dye, reactive dye, direct dye, disperse dye, cationic dye, etc. may be used. In addition, the pigment is not particularly limited and may be appropriately selected from known pigments. Among these, black pigment is particularly preferred from the viewpoint of good shielding of electromagnetic waves or infrared rays and improved identification by laser marking. Examples of black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, etc., and carbon black is preferred from the viewpoint of improving the reliability of semiconductor chips. Furthermore, these coloring agents (C) may be used alone or in combination of two or more.

The content of the component (C) is preferably 0.1 to 30 mass %, more preferably 0.5 to 25 mass %, further preferably 1.0 to 15 mass %, and further preferably 1.2 to 5 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).

<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 by the thermosetting composition (z) containing the coupling agent (D) can improve the adhesion with the sealed object. In addition, the water resistance of the cured resin film formed by thermally curing the thermosetting resin layer (Z) can also be improved without compromising the heat resistance.

The coupling agent (D) is preferably a compound that reacts with the functional group of component (A) or component (B), and more specifically, a silane coupling agent is preferred. Examples of the silane coupling agent include 3-glyceryloxypropyl trimethoxysilane, 3-glyceryloxypropyl triethoxysilane, 3-glyceryloxypropyl methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-(methacryloyloxypropyl)trimethoxysilane, 3-aminopropyl trimethoxysilane, N-6-(aminoethyl)-3-aminopropyl trimethoxysilane, N-6 -(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-butylpropyltrimethoxysilane, 3-butylpropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrahydrosulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane, etc. These coupling agents (D) may be used alone or in combination of two or more.

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

The content of the component (D) is preferably 0.01 to 10 mass %, more preferably 0.05 to 7 mass %, further preferably 0.10 to 4 mass %, and further preferably 0.15 to 2 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).

＜Inorganic filler (E)＞ The thermosetting composition (z) used in one aspect of the present invention preferably further contains an adhesive laminate from the viewpoint of producing an adhesive laminate that suppresses warpage and has a cured resin film-attached cured sealing body with a flat surface. Inorganic filler (E). The thermosetting resin layer (Z) formed of the thermosetting composition (z) containing the inorganic filler (E) can adjust the heat of the thermosetting resin layer (Z) when the sealing material is thermally cured. The degree of hardening reduces the difference in shrinkage stress between the two surfaces of the hardened sealing body. As a result, a cured sealing body with a cured resin film having a flat surface with suppressed warpage can be obtained. In addition, the thermal expansion coefficient of the cured resin film obtained by thermally curing the thermosetting resin layer (Z) can be adjusted to an appropriate range, thereby improving the reliability of the sealed object. 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., beads obtained by spheronizing these materials, single crystal fibers, glass fibers, etc., which are non-thermally expandable particles. These inorganic fillers (E) may be used alone or in combination of two or more. Among these, silica or alumina is particularly preferred from the viewpoint of being able to produce an adhesive laminate of a hardened sealant with a hardened resin film having a flat surface with suppressed warping.

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

The content of the component (E) is preferably 25 to 80 mass %, more preferably 30 to 70 mass %, further preferably 40 to 65 mass %, and further preferably 45 to 60 mass % relative to the total mass (100 mass %) of the effective ingredients of the thermosetting composition (z) or the total mass (100 mass %) of the thermosetting resin layer (Z), from the viewpoint of producing an adhesive laminate having a curable sealant with a curable resin film having a flat surface and suppressing warping.

<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 the scope that does not impair the effect of the present invention. Other additives include, for example, crosslinking agents, leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, etc. However, the total content of other additives other than components (A) to (E) is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass relative to the total amount (100% by mass) of the active ingredients of the thermosetting composition (z) or the total amount (100% by mass) of the thermosetting resin layer (Z).

[Usage method of adhesive laminate] The adhesive laminate of the present invention can fix the sealing object to the support body to perform the sealing process, and can be easily separated from the support body with a small force after the sealing process. In addition, by using the adhesive laminate, it is possible to improve productivity to manufacture a hardened seal with a hardened resin film having a flat surface and suppressing warping. Therefore, the adhesive laminate of the present invention is preferably used as follows: The sealing object is placed on the surface of the hardened resin film forming sheet (II), The aforementioned sealing object and the aforementioned surface of the hardened resin film forming sheet (II) at least on the peripheral portion of the sealing object are covered with a sealing material, and the sealing material is thermally cured to form a hardened seal containing the aforementioned sealing object.

Furthermore, in the above-mentioned method of use, it is preferred that when the aforementioned sealing material is cured, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, and the aforementioned expandable particles are expanded to separate at the interface P to obtain a cured sealant with a cured resin film.

By using the adhesive laminate of the present invention as described above, it is possible to produce a cured sealing body with a cured resin film that suppresses warpage and has a flat surface with improved productivity. Furthermore, in the above-mentioned usage method, the suitable composition of the adhesive laminate is as described above. Regarding the type of sealing material, the coating method of the sealing material, various conditions for thermal curing, etc., the following "Appendix" It is described in the item "Method for manufacturing a hardened sealing body with a hardened resin film".

[Method for manufacturing hardened sealing body with hardened resin film] A method for producing a cured sealing body with a cured resin film using the adhesive laminate of the present invention includes the following steps (i) to (iii). ･Step (i): Attach the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) included in the adhesive laminate to the support, and place the sealing object on the cured resin film forming sheet (II ) is a step that is part of the surface. ･Step (ii): Cover the front surface of the sealing object and the cured resin film-forming sheet (II) of at least the peripheral portion of the sealing object with a sealing material, and heat-harden the sealing material to form a sealing material including the sealing material. A step of forming a cured resin film by thermally curing the thermosetting resin layer (Z) while curing the sealing body of the object. ･Step (iii): A step of obtaining a hardened sealing body with a hardened resin film by expanding the aforementioned expandable particles to separate them at the interface P. Fig. 4 is a schematic cross-sectional view showing the steps of manufacturing a cured sealing body with a cured resin film using the adhesive laminate 1a shown in Fig. 1(a). Each of the above steps will be described below with appropriate reference to FIG. 4 .

＜Step (i)＞ In step (i), in order to attach the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) of the adhesive laminate to the support, the sealing object is placed on the cured resin film forming sheet (II). ) is a step that is part of the surface. In Figure 4(a), it is shown that in this step, the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) is attached to the support 50 using the adhesive laminate 1a, and is used for forming the cured resin film. The sealing object 60 is placed on a part of the surface of the thermosetting resin layer (Z) of the sheet (II). In addition, FIG. 4(a) shows an example of using the adhesive laminate 1a shown in FIG. 1(a). However, the same applies when using the adhesive laminate of the present invention having other structures. In the step, the aforementioned support, the aforementioned adhesive laminate, and the aforementioned sealing object are laminated or placed.

The temperature condition in step (i) is preferably carried out at a temperature where the expandable particles will not expand. For example, when using heat-expandable particles as expandable particles, it is sufficient as long as the expansion start temperature (t) of the heat-expandable particles does not reach, preferably in an environment of 0 to 80°C (the expansion start temperature (t) is 60 ~80℃, it is carried out in an environment that has not reached the expansion starting temperature (t).

The aforementioned support is preferably the entire surface of the adhesive surface of the adhesive layer (X) attached to the adhesive layer composite. Therefore, the support is preferably in the form of a plate. In addition, the surface area of the support on the side attached to the adhesive surface of the adhesive layer (X) is preferably greater than the area of the adhesive surface of the adhesive layer (X) as shown in FIG. 4 .

The material constituting the support is appropriately selected according to the type of sealing object or the type of sealing material used in step (ii), taking into account required characteristics such as mechanical strength or heat resistance. Specific materials constituting the support include, for example, metallic materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastics, super engineering plastics, and polyimide. Resin materials such as resin, polyamideimide resin, etc.; composite materials such as glass epoxy resin, etc. Among these, SUS, glass, and silicon wafers are particularly preferred. Furthermore, engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET). Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether sulfide (PES), and polyether ether ketone (PEEK).

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

On the other hand, examples of the sealing object placed on a part of the surface of the cured resin film forming sheet (II) include semiconductor wafers, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, Substrates for panels, etc.

For example, when the sealing object is a semiconductor wafer, by using the adhesive laminate of the present invention, a semiconductor wafer with a cured resin film can be produced. A conventionally known semiconductor chip can be used, and an integrated circuit composed of circuit elements such as transistors, resistors, capacitors, etc. is formed on the circuit surface thereof. Furthermore, the semiconductor wafer is preferably placed so that the surface of the cured resin film forming sheet (II) covers the back surface opposite to the circuit surface. At this time, after placement, the circuit surface of the semiconductor chip is exposed. For mounting the semiconductor wafer, known devices such as flip-chip bonders and die bonders can be used. The layout, arrangement number, etc. of the semiconductor chip arrangement may be appropriately determined based on the target package form, production quantity, etc.

Here, it is better to apply it to FOWLP, FOPLP, etc., where the semiconductor wafer is covered with a sealing material in an area larger than the wafer size. Not only the circuit surface of the semiconductor wafer, but also a rewiring layer is formed on the surface area of the sealing material. of packaging. Therefore, the semiconductor wafer is placed on a part of the surface of the cured resin film forming sheet (II). It is preferable to place the semiconductor wafer on the surface in a state where a plurality of semiconductor wafers are arranged at certain intervals, and more preferably A plurality of semiconductor wafers are arranged in a matrix-like state of a plurality of rows and a plurality of columns at certain intervals, and are placed on the surface. The spacing between semiconductor chips may be appropriately determined depending on the target package form, etc.

<Step (ii)> Step (ii) is a step of coating the aforementioned sealing object and the aforementioned surface of the sheet (II) for forming a hardened resin film at least on the peripheral portion of the sealing object with a sealing material (hereinafter also referred to as "coating treatment"), thermally curing the sealing material (hereinafter also referred to as "thermal curing treatment") to form a hardened sealing body including the aforementioned sealing object, and thermally curing the thermosetting resin layer (Z) to form a hardened resin film.

In the coating process of step (ii), first, at least the peripheral portion of the surface of the sealing object and the surface of the cured resin film forming sheet (II) is covered 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 wafers. For example, FIG. 4( b ) shows a state in which the sealing object 60 and the surface of the cured resin film forming sheet (II) are entirely covered with the sealing material.

Sealing materials have the function of protecting the sealed object and its accompanying elements from the external environment. The sealing material used in the manufacturing 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 granular form, sheet form, or film form, or may be in the form of a composition or liquid form. From the viewpoint of workability, sealing with a film-like sealing material is preferred. Resin film.

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

Then, after performing the coating process, the sealing material is thermally hardened to obtain a hardened sealing body in which the sealing object is sealed with the sealing material. Furthermore, the coating treatment and thermal hardening treatment in 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 thermally expandable particles is used, it is preferable that the temperature does not reach this temperature. The process is carried out under the temperature condition of the expansion starting temperature (t) of the thermally expandable particles. In addition, the coating step and the thermal hardening step can be performed separately. When the sealing material is heated in the coating step, the sealing material can be directly thermally cured by the heating, and the coating step and the thermosetting step can be performed simultaneously.

In this step, the thermosetting resin layer (Z) is thermally cured simultaneously with the thermal curing of the sealing material to form a cured resin film. In the manufacturing method of the present invention, as shown in FIG. 4(b), the thermosetting resin layer (Z) is thermally cured while being disposed on the side of the sealing object 60 sealed by the sealing material 70. Since the thermosetting resin layer (Z) is disposed, it is considered that the difference in shrinkage stress between the two surfaces of the obtained cured seal can be reduced, and the warping generated by the cured seal can be effectively suppressed.

<Step (iii)> Step (iii) is a step of obtaining a hardened seal with a hardened resin film by separating at the interface P by expanding the aforementioned expandable particles. Fig. 4(c) shows the state of separation at the interface P by expanding the expandable particles. As shown in Fig. 4(c), by separating at the interface P, a hardened seal 80 having a sealed object 60 and a hardened resin film (Z') formed by heat-curing the thermosetting resin layer (Z) can be obtained. Furthermore, the presence of the hardened resin film (Z') has the function of effectively suppressing the warping generated in the hardened seal, and protects the sealed object, which helps to improve the reliability of the sealed object.

The "expansion treatment" in step (iii) is performed depending on the type of expandable particles used. For example, when thermally expandable particles are used, the thermally expandable particles are expanded by heating above the thermal expansion starting temperature (t), whereby the surface of the adhesive sheet (I) on the side of the cured resin film forming sheet (II) is Create bumps. As a result, the interface P can be easily separated together with a small force. The "temperature above the expansion start temperature (t)" when expanding the heat-expandable particles is preferably above the "expansion start temperature (t) + 10°C" and below the "expansion start temperature (t) + 60°C" ; More preferably, it is "expansion start temperature (t) + 15°C" or more and "expansion start temperature (t) + 40°C" or less. Furthermore, from the viewpoint of making it easy to separate 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 hardened seal with the hardened resin film obtained in this way can then be ground until the electrical surface of the semiconductor chip is exposed, and then the electrical surface can be rewired, or external electrode pads can be formed, and the external electrode pads can be connected to external terminal electrodes. In addition, after the external terminal electrodes are connected to the hardened seal, they can be singulated to manufacture semiconductor devices. [Example]

The present invention is specifically illustrated by 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.

<Mass average molecular weight (Mw)> The value is measured using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name "HLC-8020") under the following conditions and converted to standard polystyrene. (Measurement conditions) ･Column: "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", "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> Measurement was performed using a constant pressure thickness tester manufactured by Teclock Co., Ltd. (model: "PG-02J", standard specification: in accordance with JIS K6783, Z1702, Z1709).

<Storage modulus E' of the expansive substrate layer (Y1)> The expansive substrate layer (Y1) was formed to a size of 5 mm in length × 30 mm in width × 200 μm in thickness, and the peeling material was removed as a test sample. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), the storage modulus E' of the test sample at a specific temperature was measured under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, a vibration frequency of 1 Hz, and an amplitude of 20 μm.

<Shear storage modulus G' of adhesive layers (X1) and (X2)> The formed adhesive layers (X1) and (X2) were cut into 8mm diameter circles, the peeling material was removed and stacked to form a 3mm thick test sample. The shear storage modulus G' of the test sample at a specific temperature was measured by the torsional shear method under the conditions of test start temperature 0℃, test end temperature 300℃, temperature rise rate 3℃/min, and vibration frequency 1Hz.

<Storage modulus E’ of the cured resin film after thermal curing of the thermosetting resin layer (Z)> After laminating the thermosetting resin layer (Z) to a thickness of 200 μm, it is placed in an oven in an atmospheric environment and heated at 130°C for 2 hours to thermally harden the thermosetting resin layer (Z) with a thickness of 200 μm. Becomes a hardened resin film. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), the measurement was performed under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a temperature rise rate of 3°C/min, a vibration frequency of 11Hz, and an amplitude of 20μm. Storage modulus E' of the hardened resin film formed at 23°C.

<Probe viscosity value> Cut the substrate to be measured into squares with a side of 10 mm and place them in an environment of 23°C and 50% RH (relative humidity) for 24 hours to prepare the test sample. Use a probe viscosity tester (manufactured by Tester Industrial Co., Ltd., product name "TE-6001") to measure the probe viscosity value on the surface of the test sample in an environment of 23°C and 50% RH (relative humidity) according to JIS Z0237:1991. Specifically, a stainless steel probe with a diameter of 5 mm is brought into contact with the surface of the test sample with a contact load of 0.98 N/ ^cm2 for 1 second. The force required to remove the probe from the surface of the test sample at a speed of 10 mm/second is measured, and the value obtained is used as the probe viscosity value of the test sample.

<Measurement of Adhesion> A PET film with a thickness of 50 μm (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4100") was laminated on the surface of the adhesive layer or thermosetting resin layer (Z) formed on the release film. The release film was then removed, and the exposed surface of the adhesive layer or thermosetting resin layer (Z) was attached to a stainless steel plate (SUS304 360 polished) as an adherend. After being left at 23°C and 50% RH (relative humidity) for 24 hours, the adhesion at 23°C was measured in the same environment by the 180° peeling method at a tensile speed of 300 mm/min based on JIS Z0237:2000.

Preparation Example 1 (Synthesis of Urethane Prepolymer) In a reaction vessel under a nitrogen environment, 100 parts by weight (solid content ratio) of polycarbonate diol having a mass average molecular weight of 1,000 is mixed with isophorone diisocyanate so that the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of isophorone diisocyanate becomes 1/1. 160 parts by weight of toluene is further added, and the mixture is stirred under a nitrogen environment and reacted at 80°C for more than 6 hours until the isocyanate group concentration reaches the theoretical amount. Next, a solution prepared by diluting 1.44 parts by weight (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by weight of toluene was added, and the mixture was further reacted at 80°C for 6 hours until the isocyanate groups at both ends were eliminated, thereby obtaining a urethane prepolymer having a mass average molecular weight of 29,000.

Production Example 2 (Synthesis of Acrylic Urethane Resin) In a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solid content ratio) of the urethane prepolymer obtained in Production Example 1, 117 parts by mass (solid content ratio) of methyl methacrylate (MMA), and 5.1 parts by mass (solid content ratio) of 2-hydroxyethyl acrylate (2-HEMA), 1.1 parts by mass (solid content ratio) of 1-thioglycerol, and 50 parts by mass of toluene were heated to 105°C while stirring. Then, a solution obtained by diluting 2.2 parts by mass (solid content ratio) of a radical initiator (manufactured by Nippon Finechem Co., Ltd., product name "ABN-E") with 210 parts by mass of toluene was maintained at 105°C. It was dripped into the reaction vessel over 4 hours. After completion of the dropping, the reaction was carried out at 105° C. for 6 hours to obtain a solution of an acrylic urethane resin with a mass average molecular weight of 105,000.

Production Example 3 (Preparation of thermosetting composition) Blend each component of the type and blending amount (all are "active ingredient ratios") shown below, further dilute it with methyl ethyl ketone, and stir evenly to prepare a solid content concentration (active ingredient concentration) of 61 mass % solution of hardening composition. ･Acrylic polymer: blending amount = 26.07 parts by mass An acrylic polymer (mass average molecular weight) 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 : 400,000, glass transition temperature: -1℃), equivalent to the above component (A1). ･Epoxy compound (1): Blending amount = 10.4 parts by mass Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "jER828", epoxy equivalent = 184 to 194 g/eq) is equivalent to the above component (B1). ･Epoxy compound (2): Blending amount = 5.2 parts by mass Dicyclopentadiene-type epoxy resin (manufactured by DIC Co., Ltd., product name "Epiclon HP-7200HH", epoxy equivalent = 255 to 260 g/eq) is equivalent to the above component (B1). ･Epoxy compound (3): Blending amount = 1.7 parts by mass Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., product name "jER1055", epoxy equivalent = 800 to 900g/eq) is equivalent to the above component (B1). ･Thermal hardener: blending amount = 0.42 parts by mass Dicyanodiamide (manufactured by ADEKA, product name "Adeka Hardener EH-3636AS", active hydrogen content = 21 g/eq) is equivalent to the above component (B2). ･Harding accelerator: blending amount = 0.42 parts by mass 2-Phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "Curezol 2PHZ") is equivalent to the above component (B3). ･Coloring agent: Blending amount = 0.20 parts by mass Carbon black (manufactured by Mitsubishi Chemical Co., Ltd., product name "#MA650", average particle diameter = 28 nm) corresponds to the above component (C). ･Silane coupling agent: blending amount = 0.09 parts by mass 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM403"), molecular weight = 236.64, is equivalent to the above component (D). ･Inorganic filler: Blending amount = 55.5 parts by mass Silica filler (manufactured by Admatechs, product name "SC2050MA", average particle diameter = 0.5 μm) corresponds to the above component (E).

The details of the adhesive resin, additive, thermally expandable particles, and release material used in the formation of each layer in the following embodiments are as described below.

＜Adhesive resin＞ ･Acrylic copolymer (i): One of the constituent units derived from raw material monomers consisting of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) Acrylic copolymer with Mw600,000. ･Acrylic copolymer (ii): has the properties of n-butyl acrylate (BA)/methyl methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid=86.0/8.0/5.0/1.0( Mass ratio) acrylic copolymer with a structural unit of raw material monomers of Mw 600,000.

＜Additive＞ ･Isocyanate cross-linking agent (i): Made by Tosoh Co., Ltd., product name "Coronate L", solid content concentration: 75 mass%.

<Thermal expandable particles> ･Thermal expandable particles (i): Made by Kureha Co., Ltd., product name "S2640", expansion starting temperature (t) = 208°C, average particle diameter (D ₅₀ ) = 24 μm, 90% particle diameter (D ₉₀ )=49μm.

<Release material> Heavy-duty release film: A polyethylene terephthalate (PET) film with a release layer formed of a polysilicone release agent on one side, manufactured by Lintec Co., Ltd., product name "SP-PET382150", thickness: 38μm. Light-duty release film: A PET film with a release layer formed of a polysilicone release agent on one side, manufactured by Lintec Co., Ltd., product name "SP-PET381031", thickness: 38μm.

Example 1 An adhesive laminate 2b shown in FIG. 2(b) is prepared by the following sequence, wherein a release material is further laminated on the second adhesive layer (X2) of the adhesive sheet (I) and the thermosetting resin layer (Z) of the sheet (II) for forming a curable resin film. [1] Preparation of Adhesive Sheet (I) (1-1) Formation of First Adhesive Layer (X1) 100 parts by weight of the solid content of the acrylic copolymer (i) of the adhesive resin was mixed with 5.0 parts by weight of the isocyanate crosslinking agent (i) (solid content ratio), diluted with toluene, and uniformly stirred to prepare an adhesive composition having a solid content concentration (active ingredient concentration) of 25% by weight. Then, the adhesive composition was applied to the surface of the release 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 first adhesive layer (X1) of a non-thermal expansion adhesive layer having a thickness of 5 μm. Furthermore, at 23° C., the shear storage modulus G′(23) of the first adhesive layer (X1) was 2.5×10 ⁵ Pa. Furthermore, the adhesive force of the first adhesive layer (X1) measured by the above method was 0.3 N/25 mm.

(1-2) Formation of the second adhesive layer (X2) 100 parts by weight of the solid content of the acrylic copolymer (ii) of the adhesive resin was mixed with 0.8 parts by weight of the isocyanate crosslinking agent (i) (solid content ratio), diluted with toluene, and uniformly stirred to prepare an adhesive composition having a solid content concentration (active ingredient concentration) of 25% by weight. Then, the adhesive composition was applied to the surface of the peeling agent layer of the light peeling film to form a coating film, and the coating film was dried at 100°C for 60 seconds to form a second adhesive layer (X2) having a thickness of 10 μm. Furthermore, at 23° C., the shear storage modulus G′(23) of the second adhesive layer (X2) was 9.0×10 ⁴ Pa. Furthermore, the adhesive force of the second adhesive layer (X2) measured by the above method was 1.0 N/25 mm.

(1-3) Preparation of base material (Y) To 100 parts by mass of the solid content of the acrylic urethane resin obtained in Production Example 2, 6.3 parts by mass (solid content ratio) of the above-mentioned isocyanate cross-linking agent (i) and bis(2-ethyl) as a catalyst were blended. 1.4 parts by mass of dioctyltin ylhexanoate (solid content ratio) and the thermally expandable particles (i) mentioned above were diluted with toluene and stirred uniformly to prepare a resin composition with a solid content concentration (active ingredient concentration) of 30 mass %. In addition, the content of the thermally expandable particles (i) was 20 mass% with respect to the total amount of active ingredients (100 mass%) in the obtained resin composition. Then, on the surface of a 50 μm-thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4100", probe viscosity value: 0 mN/5mmφ) of a non-thermally expandable base material On, the resin composition was applied to form a coating film, and the coating film was dried at 100° C. for 120 seconds to form an expandable base material layer (Y1) with a thickness of 50 μm. Here, the PET film of the non-thermally expandable base material corresponds to the non-expandable base material layer (Y2). As above, the base material (Y) consisting of the expandable 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.

Furthermore, as a sample for measuring the physical property values of the expandable substrate layer (Y1), the resin composition was applied to the surface of the peeling agent layer of the above-mentioned light peeling film to form a coating film, and the coating film was dried at 100°C for 120 seconds to similarly form an expandable substrate layer (Y1) with a thickness of 50μm. Then, based on the above-mentioned measurement method, the storage modulus and probe viscosity value of the expandable substrate layer (Y1) at each temperature were measured. The measurement results are as follows. ･Storage modulus at 23℃E'(23)=2.0×10 ⁸ Pa ･Storage modulus at 100℃E'(100)=3.0×10 ⁶ Pa ･Storage modulus at 208℃E'(208)=5.0×10 ⁵ Pa ･Probe viscosity value=0mN/5mmφ

(1-4)Lamination of each layer The non-expanding base material layer (Y2) of the base material (Y) produced in the above (1-3) is bonded to the second adhesive layer (X2) formed in the above (1-2), and the The expandable base material layer (Y1) is bonded to the first adhesive layer (X1) formed in the above (1-1). Then, the light peeling film/second adhesive layer (X2)/non-expanding base material layer (Y2)/expanding base material layer (Y1)/first adhesive layer (X1)/heavy peeling are laminated in this order. Adhesive sheet made of thin film (I).

[2] Preparation of the sheet (II) for forming a cured resin film. The solution of the curable composition prepared in Production Example 3 is applied on the peeling surface of the above-mentioned light peeling film to form a coating film. The coating film is dried at 120 °C for 2 minutes to form a thermosetting resin layer (Z) with a thickness of 25 μm, and a cured resin film forming sheet (II) composed of the thermosetting resin layer (Z) and a light peeling film was produced. Furthermore, the adhesive force of the formed thermosetting resin layer (Z) is 0.5N/25mm. Furthermore, the storage modulus E' of the cured resin film after thermosetting of the thermosetting resin layer (Z) is 6.5×10 ⁹ Pa.

[3] Preparation of adhesive laminate Remove the heavy peeling film of the adhesive sheet (I) produced in the above [1], and separate the exposed first adhesive layer (X1) and the exposed thermosetting resin layer (Z) of the cured resin film forming sheet (II). ) are bonded to the surface to obtain an adhesive laminate.

This adhesive laminate was measured based on the following method when the interface P between the first adhesive layer (X1) of the adhesive sheet (I) and the cured resin film-forming sheet (II) separated before and after the expansion treatment, that is, the heat treatment. Peeling force (F ₀ ), (F ₁ ). As a result, the peeling force when separating from the interface P before heat treatment (F ₀ ) = 200mN/25mm, and the peeling force when separating from the interface P after heat treatment (F ₁ ) = 0mN/25mm, the peeling force (F ₁ ) to the peeling force (F ₀ ) [(F ₁ )/(F ₀ )] is 0.

<Determination of peeling force (F ₀ )> After the prepared adhesive laminate was placed in an environment of 23°C and 50% RH (relative humidity) for 24 hours, the peeling film on the adhesive sheet (I) side of the adhesive laminate was removed, and the exposed second adhesive layer (X2) was attached to a stainless steel plate (SUS304, 360 polishing). Then, the end of the stainless steel plate attached with the adhesive laminate was fixed to the lower chuck of a universal tensile testing machine (manufactured by Orientec, product name "Tensilon UTM-4-100"). Furthermore, the sheet (II) for forming a hardened resin film of the adhesive laminate is fixed by the upper chuck of the universal tensile testing machine so that the interface P between the first adhesive layer (X1) of the adhesive sheet (I) of the adhesive laminate and the sheet (II) for forming a hardened resin film is peeled off. Then, under the same environment as above, based on JIS Z0237:2000, the peeling force measured at the time of peeling off at the interface P by the 180° peeling method at a tensile speed of 300 mm/min is taken as the "peeling force (F ₀ )".

<Measurement of Peeling Force (F ₁ )> Remove the light peeling film on the adhesive sheet (I) side of the produced adhesive laminate, and attach the exposed second adhesive layer (X2) to a stainless steel plate (SUS304, 360 grind). Then, the stainless steel plate and the adhesive laminate were heated at 240°C for 3 minutes to expand the thermally expandable particles in the thermally expandable base material layer (Y1) of the adhesive laminate. Thereafter, in the same manner as the measurement of the peeling force (F ₀ ), the interface P between the first adhesive layer (X1) of the adhesive sheet (I) and the cured resin film forming sheet (II) is peeled under the above conditions. The measured peeling force is referred to as "peeling force (F ₁ )". Furthermore, in the measurement of the peeling force (F ₁ ), when trying to fix the cured resin film-forming sheet (II) of the adhesive laminate with the upper chuck of the universal tensile testing machine, if the cured resin film-forming sheet (II) II) When the interface P is completely separated and cannot be fixed, the measurement is terminated, and the peeling force (F ₁ ) at this time is regarded as "0mN/25mm".

Example 2 Through the following procedures, a cured sealing body with a cured resin film is produced. (1) Placement of semiconductor chips The light peeling film on the adhesive sheet (I) side of the adhesive laminate produced in Example 1 was removed, and the adhesive surface of the second adhesive layer (X2) of the exposed adhesive sheet (I) was separated from the support ( glass) attached. Then, the light peeling film on the side of the sheet (II) for forming the cured resin film was also removed, and 9 semiconductor wafers (each wafer size was 6.4 mm × 6.4 mm, and the wafer thickness was 200 μm (♯2000)) were separated from each other. The wafer is placed on the exposed surface of the thermosetting resin layer (Z) with a necessary distance between the back surface opposite to the circuit surface and the surface in contact with the surface.

(2) Formation of a hardened seal The nine semiconductor chips and the surface of the thermosetting resin layer (Z) at least at the periphery of the semiconductor chips are coated with a thermosetting resin film of a sealing material, and the sealing resin film is thermally hardened using a vacuum heating and pressure laminator ("7024HP5" manufactured by ROHM and HAAS) to produce a hardened seal. The sealing conditions are as follows. ･Preheating temperature: 100℃ for both the base and the diaphragm ･Evacuation: 60 seconds ･Dynamic pressing mode: 30 seconds ･Static pressing mode: 10 seconds ･Sealing temperature: 180℃×60 minutes Furthermore, along with the thermal curing of the sealing resin film, the thermosetting resin layer (Z) of the sheet (II) for forming the cured resin film is also cured in the above environment to form a cured resin film.

(3) Separation at interface P After the above (2), heat treatment is performed for 3 minutes at 240°C or higher than the expansion start temperature (208°C) of the thermally expandable particles. Then, the interface P between the first adhesive layer (X1) of the adhesive sheet (I) and the cured resin film formed by thermosetting the thermosetting resin layer (Z) of the cured resin film forming sheet (II) can be Easily separated together. After separation at the interface P, a hardened sealing body with a hardened resin film can be obtained. Furthermore, the obtained cured sealing body with the cured resin film was cooled to room temperature (25° C.), but no warpage was observed.

1a, 1b, 2a, 2b, 3‧‧‧Adhesive laminate (I)‧‧‧Adhesive flakes (X)‧‧‧Adhesive layer (X1)‧‧‧1st adhesive layer (X2)‧‧‧Second adhesive layer (Y)‧‧‧Substrate (Y1)‧‧‧Thermal expandable base material layer (Y2)‧‧‧Non-thermal expandable base material layer (II)‧‧‧Sheet for forming cured resin film (Z)‧‧‧Thermosetting resin layer (Z’)‧‧‧hardened resin film P‧‧‧The interface between the adhesive sheet (I) and the cured resin film forming sheet (II) 50‧‧‧Support 60‧‧‧Sealed objects 70‧‧‧Sealing material 80‧‧‧hardened sealing body 100‧‧‧Hardened sealing body with hardened resin film

[FIG. 1] is a schematic cross-sectional view showing the adhesive laminate of the first embodiment of the present invention. [FIG. 2] is a schematic cross-sectional view showing the adhesive laminate of the second embodiment of the present invention. [FIG. 3] is a schematic cross-sectional view showing the adhesive laminate of the third embodiment of the present invention. [FIG. 4] is a schematic cross-sectional view showing the step of manufacturing a hardened sealant with a hardened resin film using the adhesive laminate 1a shown in FIG. 1(a).

1a, 1b‧‧‧Adhesive laminate

(I)‧‧‧Adhesive sheet

(X)‧‧‧Adhesive layer

(Y)‧‧‧Substrate

(Y1)‧‧‧Thermal expandable base material layer

(Y2)‧‧‧Non-thermal expansion base layer

(II)‧‧‧Sheet for forming cured resin film

(Z)‧‧‧Thermosetting resin layer

P‧‧‧Interface between adhesive sheet (I) and hardened resin film forming sheet (II)

Claims (15)

An adhesive laminate having a base material (Y) and an adhesive layer (X), an expandable adhesive sheet (I) containing expandable particles in any layer, and a thermosetting resin layer (Z ), an adhesive laminate consisting of a sheet (II) for forming a cured resin film, an adhesive sheet (I), and a thermosetting resin layer (Z) of the sheet (II) for forming a cured resin film directly laminated, wherein The base material (Y) has an expandable base material layer (Y1) containing expandable particles, and is formed at the interface between the adhesive sheet (I) and the cured resin film forming sheet (II) by expanding the aforementioned expandable particles. P separation. The adhesive laminate of claim 1, wherein the expandable particles are thermally expandable particles. The adhesive laminate of claim 1 or 2, wherein the thermosetting resin layer (Z) is formed of a thermosetting composition (z) containing a polymer component (A) and a thermosetting component (B). layer. The adhesive laminate of claim 1 or 2 has the following structure: the adhesive layer (X) of the adhesive sheet (I) is composed of the first adhesive layer (X1) and the second adhesive layer (X2), and the first adhesive layer (X1) and the second adhesive layer (X2) sandwich the substrate (Y), and the adhesive surface of the first adhesive layer (X1) is directly laminated with the thermosetting resin layer (Z). The adhesive composite of claim 1 or 2, wherein the adhesive layer (X) is a non-expandable adhesive layer. The adhesive laminate of claim 1 or 2, wherein the base material (Y) has an expanding base material layer (Y1) and a non-expanding base material layer (Y2). The adhesive laminate of claim 6 has a first adhesive layer (X1) laminated on the surface of the expandable base material layer (Y1), and a second adhesive layer (X2) laminated on the non-expandable base material layer (Y1). The composition on the surface of the base material layer (Y2). The adhesive layer composite of claim 7, wherein the first adhesive layer (X1) and the second adhesive layer (X2) are non-expandable adhesive layers. As in claim 1 or 2, the adhesive laminate, wherein the sheet (II) for forming the hardened resin film is composed only of the thermosetting resin layer (Z). The adhesive laminate of claim 1 or 2 is used for placing a sealing object on the surface of a hardened resin film forming sheet (II), and covering the aforementioned sealing object and the aforementioned surface of the hardened resin film forming sheet (II) at least at the periphery of the sealing object with a sealing material, and thermally curing the sealing material to form a hardened sealing body including the aforementioned sealing object. For example, the adhesive laminate of claim 10 is used to heat cure the aforementioned sealing material, and the thermosetting resin layer (Z) is also heat cured to form a hardened resin film. By expanding the aforementioned expandable particles, they are separated at the interface P to obtain a hardened sealing body with a hardened resin film. The adhesive laminate according to claim 1 or 2, wherein the expandable base material layer (Y1) is made of a resin containing at least one selected from the group consisting of acrylic urethane resin and olefin resin, and the aforementioned expandable particles. Composition (y) is formed. A method of using an adhesive laminate according to any one of Claims 1 to 12, wherein a sealing object is placed on the surface of the cured resin film forming sheet (II), and The aforementioned sealing object and the front surface of the cured resin film forming sheet (II) of at least the peripheral portion of the sealing object are covered with a sealing material, and the sealing material is thermally cured to form a cured seal including the aforementioned sealing object. body. The method of using an adhesive laminate according to Claim 13, wherein when the sealing material is cured, the thermosetting resin layer (Z) is also thermally cured to form a cured resin film, and the expandable particles are expanded by the process. , separated at the interface P, obtaining a hardened sealing body with a hardened resin film. A method of manufacturing a cured sealing body with a cured resin film, which is a method of manufacturing a cured sealing body with a cured resin film using the adhesive laminate according to any one of claims 1 to 12, which has the following Steps (i)~(iii);. Step (i): Attach the adhesive surface of the adhesive layer (X) of the adhesive sheet (I) included in the adhesive laminate to the support, and place the sealing object on the cured resin film forming sheet (II) The steps of part of the surface. Step (ii): Cover the aforementioned sealing object and the front surface of the cured resin film-forming sheet (II) of at least the peripheral portion of the sealing object with a sealing material, and heat-harden the sealing material to form a sealing object. The step of forming a cured sealing body of the object and also thermally curing the thermosetting resin layer (Z) to form a cured resin film. Step (iii): A step of obtaining a hardened sealing body with a hardened resin film by separating the expandable particles at the interface P by expanding the aforementioned expandable particles.