KR102543787B1 - Manufacturing method of laminate and curing encapsulation - Google Patents

Abstract

An energy ray-curable resin layer (I) and a support layer (II) supporting the energy ray-curable resin layer (I), wherein the energy ray-curable resin layer (I) has an adhesive surface, the support layer ( II) has a base material (Y) and an adhesive layer, and at least one of the base material (Y) and the pressure-sensitive adhesive layer contains thermally expandable particles, and a cured resin layer obtained by curing the energy ray-curable resin layer (I) ( It is related with the laminated body in which I') and the said support layer (II) are separated at the interface by the process which expands the said thermally expansible particle.

Description

Manufacturing method of laminate and curing encapsulation

The present invention relates to a method for producing a laminate and a curing encapsulated body.

BACKGROUND ART In recent years, miniaturization, weight reduction, and high functionality of electronic devices are progressing, and semiconductor chips are sometimes mounted in packages close to the size. Such a package may be referred to as CSP (Chip Scale Package). Examples of the CSP include Wafer Level Package (WLP), which completes the final package process in a wafer size, and Panel Level Package (PLP), which completes the package final process in a panel size larger than the wafer size.

WLP and PLP are classified into fan-in type and fan-out type. In the fan-out type WLP (hereinafter also referred to as "FOWLP") and PLP (hereinafter also referred to as "FOPLP"), a semiconductor chip is covered with an encapsulant so as to have an area larger than the chip size, and the semiconductor chip is cured and encapsulated. and a redistribution layer and external electrodes are formed not only on the circuit surface of the semiconductor chip but also on the surface region of the encapsulant.

FOWLP and FOPLP are, for example, a mounting step of placing a plurality of semiconductor chips on a sheet for temporary fixing, a coating step of coating with a thermosetting encapsulant, and curing to obtain a cured encapsulant by thermally curing the encapsulant. It is manufactured through a process, a separation process of separating the curing encapsulation body from the temporary fixing sheet, and a redistribution layer formation process of forming a redistribution layer on the surface of the exposed semiconductor chip (hereinafter, processing performed in the coating process and curing process). is also referred to as “encapsulation processing”).

Patent Literature 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporarily fixing at the time of cutting an electronic component, in which a heat-expandable adhesive layer containing heat-expandable microspheres is formed on at least one side of a base material. In the production of FOWLP and FOPLP, it is also conceivable to use the heat-peelable pressure-sensitive adhesive sheet described in Patent Literature 1.

Japanese Patent Publication No. 3594853

However, when a cured encapsulated body is produced using the pressure-sensitive adhesive sheet described in Patent Literature 1 as a sheet for temporarily fixing, the cured encapsulated body tends to warp due to thermal contraction. This is because the semiconductor chips sealed in the curing encapsulation body are biased toward the side in contact with the sheet for temporarily fixing, so in the curing encapsulation body, the region where the ratio of semiconductor chips with a small thermal expansion coefficient is relatively high, This is considered to be because a region having a relatively high proportion of the cured resin having a large thermal expansion coefficient is generated, and stress is generated due to a difference in thermal contraction rate between the two regions. This problem tends to become more conspicuous as the size of a package such as FOWLP or FOPLP increases.

The cured encapsulated body that has warped is prone to cracking when grinding the cured encapsulated body in the next step, for example, and the curing encapsulated body by the arm when conveying the cured encapsulated body by the device There may be harmful effects, such as the fact that it is easy to cause problems at the time of delivery.

As a method of suppressing the curvature of the cured encapsulated body, for example, a method of using a laminate comprising a temporarily fixed layer and a thermosetting resin layer formed with a thermally expandable adhesive layer containing thermally expandable particles can also be considered. That is, after carrying out the semiconductor chip mounting step and the coating step on the thermosetting resin layer provided by the laminate, and then thermosetting the thermosetting resin layer and the encapsulating material to obtain a cured encapsulation body with a cured resin layer, It is a method of foaming thermally expansible particles and separating the cured encapsulation body with the cured resin layer and the temporarily fixed layer. According to this method, since the cured resin layer functions as a curvature preventing layer of the cured encapsulated body, a cured encapsulated body in which the occurrence of warpage is suppressed is obtained.

On the other hand, according to the above method, since the treatment for foaming the thermally expandable particles and the treatment for curing the thermosetting resin layer are both heat treatments, during the heat treatment for curing the thermosetting resin layer, the There are cases where the thermally expandable particles are foamed. According to the study of the present inventors, etc., before the thermally curable resin layer is sufficiently cured, when the thermally expandable particles in the temporarily fixed layer are foamed, it has been found that the separability of the temporarily fixed layer deteriorates in the subsequent separation step.

Therefore, while applying the cured resin layer as the warpage prevention layer to the cured encapsulation body, after forming the cured encapsulation body with the cured resin layer, the cured resin layer and the temporarily fixed layer can be easily separated. Use for production of a cured encapsulation body Possible laminates are desired.

In view of the above problems, the present invention has a support layer and a curable resin layer, and can fix an object to be sealed to the surface of the curable resin layer to perform a sealing process, and a cured sealing body formed by the sealing process. An object of the present invention is to provide a laminate capable of providing a cured resin layer as a warp prevention layer and easily separating the cured resin layer and the support layer, and a method for manufacturing a cured encapsulated body using the laminate.

MEANS TO SOLVE THE PROBLEM The inventors of the present invention, as a result of earnest research so as to be able to solve the above-mentioned problems, discovered that the above-mentioned problems could be solved by the present invention described below, and came to complete the present invention.

That is, the present invention relates to the following [1] to [11].

[1] an energy ray-curable resin layer (I),

a support layer (II) supporting the energy ray-curable resin layer (I);

The energy ray-curable resin layer (I) has an adhesive surface,

The support layer (II) has a base material (Y) and an adhesive layer (X), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (X) contains thermally expandable particles,

A laminate in which a cured resin layer (I′) formed by curing the energy ray-curable resin layer (I) and a support layer (II) are separated at the interface by a treatment for expanding the thermally expandable particles.

[2] The storage modulus (E') at 23°C of the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) is 1.0 × 10 ⁷ to 1.0 × 10 ¹³ Pa, the above [ 1].

[3] The laminate according to [1] or [2] above, wherein the energy ray-curable resin layer (I) has a thickness of 1 to 500 µm.

[4] The laminate according to any one of [1] to [3] above, wherein the visible light transmittance of the energy ray-curable resin layer (I) is 5% or more.

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

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

[7] The laminate according to [5] or [6], wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.

[8] The substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1),

The support layer (II) has a non-expandable substrate layer (Y2), an expandable substrate layer (Y1), and an adhesive layer (X) in this order,

The laminate according to any one of [5] to [7] above, in which the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.

[9] An object to be sealed is placed on a part of the surface of the energy ray-curable resin layer (I),

The energy ray-curable resin layer (I) is irradiated with energy rays to form a cured resin layer (I′) formed by curing the energy ray-curable resin layer (I);

Covering the surface of the object to be sealed and the cured resin layer (I′) of at least the periphery of the object to be sealed with a thermosetting sealing material;

After the encapsulant is thermally cured, the cured resin layer (I′) and the support layer (II) are separated at the interface by a process of expanding the thermally expansible particles to form a cured encapsulant containing the object to be encapsulated. The laminate according to any one of the above [1] to [8], which is used to do so.

[10] The laminate according to the above [9], which is used to prevent warping of the curing encapsulated body.

[11] A method for producing a cured encapsulated body using the laminate according to any one of [1] to [10] above, comprising the following steps (i) to (iv).

Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate

Step (ii): Step of forming a cured resin layer (I′) obtained by curing the energy ray-curable resin layer (I) by irradiating the energy ray-curable resin layer (I) with an energy ray

Step (iii): Covering the surfaces of the object to be sealed and the cured resin layer (I′) at least around the object to be sealed with a thermosetting encapsulant, and curing the encapsulant by heat, including the object to be encapsulated Process of forming cured encapsulation

Step (iv): Step of separating the cured resin layer (I′) and the support layer (II) at the interface by the treatment of expanding the thermally expandable particles to obtain a cured encapsulated body with a cured resin layer

According to the present invention, it has a support layer and a curable resin layer, and it is possible to perform sealing processing by fixing the object to be sealed on the surface of the curable resin layer, and the cured sealing body formed by the sealing processing can be cured as an anti-warping layer It is possible to provide a laminate capable of providing a base layer and easily separating the cured resin layer and the support layer, and a method of manufacturing a cured encapsulated body using the laminate.

1 is a schematic cross-sectional view of the laminate of the first aspect of the present invention, showing the structure of the laminate.
Fig. 2 is a cross-sectional schematic view of the laminate of the second aspect of the present invention showing the configuration of the laminate.
Fig. 3 is a schematic cross-sectional view of the laminate of the third aspect of the present invention, showing the configuration of the laminate.
Fig. 4 is a cross-sectional schematic view showing a step of manufacturing a cured encapsulated body with a cured resin layer using the layered product 1a shown in Fig. 1(a).
Fig. 5 is a schematic cross-sectional view showing a method for processing a curing encapsulated body.

In this specification, whether or not the target layer is a "non-expandable layer" is determined by the case where the volume change rate calculated from the following formula before and after the treatment is less than 5% after the treatment for expansion is performed for 3 minutes. The layer is judged to be a "non-expandable layer". On the other hand, when the volume change rate is 5% or more, the layer is judged to be an "expandable layer".

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

In the case of a layer containing thermally expandable particles, for example, as the "expanding treatment", heat treatment may be performed at the expansion start temperature (t) of the thermally expandable particles for 3 minutes.

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

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

In this specification, for example, "(meth)acrylic acid" shows both "acrylic acid" and "methacrylic acid", and other similar terms are also the same.

In this specification, the lower limit value and upper limit value described step by step for a preferred numerical range (for example, ranges such as content) can be combined independently of each other. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", "preferably lower limit (10)" and "more preferable upper limit (60)" are combined to "10 to 60" You may.

Unless otherwise indicated, each component and material exemplified in this specification may be used alone or in combination of two or more, and in the case of a combination of two or more, their combination and ratio are arbitrarily selected. can

In this specification, an "energy ray" means an electromagnetic wave or a charged particle beam having energy quanta, and examples thereof include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, or an LED lamp as an ultraviolet light source. Electron beams can be irradiated with those generated by an electron beam accelerator or the like.

In this specification, “energy ray curability” means a property that is cured by irradiation with energy rays, and “non-energy ray curability” means a property that is not cured even when irradiated with energy rays.

[Laminate]

A laminate of one aspect of the present invention includes an energy ray-curable resin layer (I) and a support layer (II) supporting the energy ray-curable resin layer (I).

The energy ray-curable resin layer (I) has an adhesive surface.

The support layer (II) has a base material (Y) and an adhesive layer (X), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (X) contains thermally expandable particles.

In the laminate of one aspect of the present invention, a cured resin layer (I′) obtained by curing an energy ray-curable resin layer (I) by a treatment of expanding thermally expandable particles in the support layer (II) and a support layer (II) are formed. , can be separated at that interface. In short, in the laminate of one embodiment of the present invention, thermally expandable particles expand by thermal expansion treatment, and irregularities are formed on the surface of the layer containing the thermally expandable particles, and the support layer (II) and the energy ray-curable resin layer The contact area with the cured resin layer (I') obtained by curing (I) is reduced. As a result, at the interface between the support layer (II) and the cured resin layer (I'), they can be collectively and easily separated with a slight force.

In addition, since the laminate of one embodiment of the present invention does not need to be heated when curing the energy ray-curable resin layer (I), heat in the support layer (II) is reduced when the energy ray-curable resin layer (I) is cured. The expandable particles do not expand, resulting in excellent separability between the support layer (II) and the cured resin layer (I') formed by curing the energy ray-curable resin layer (I).

In the laminate of one aspect of the present invention, an object to be sealed is placed on a part of the surface of the energy ray-curable resin layer (I), and energy ray-curable resin layer (I) is irradiated with energy rays to obtain an energy ray-curable resin layer ( I) is formed by curing the cured resin layer (I'), the surface of the object to be sealed and the cured resin layer (I') at least around the object to be sealed is coated with a thermosetting sealing material, After thermally curing the material, the cured resin layer (I') and the support layer (II) are separated at the interface by the treatment of expanding the thermally expandable particles to form a cured encapsulation body containing the object to be encapsulated. It is preferable to use

The cured encapsulated body formed by the above method becomes one provided with a cured resin layer (I') on the surface of the side where the proportion of semiconductor chips is relatively high. As a result, the difference in shrinkage stress between the two surfaces of the cured encapsulated body can be reduced, and a cured encapsulated body in which warpage is effectively suppressed can be obtained.

That is, the laminate of one aspect of the present invention is useful as a laminate for preventing warpage, which is used to prevent warping of a curing encapsulated body.

At that time, since the laminate of one aspect of the present invention has an energy ray-curable resin layer (I), which is easier to adjust to increase the adhesive force than the thermosetting resin layer, the object to be sealed can be more reliably fixed to a part of the surface. can In addition, when the thermosetting resin layer is heated at a high temperature, it softens mainly in the initial stage of curing, and thus may cause chip misalignment. Therefore, it is possible to avoid chip displacement accompanying hardening.

<Configuration of laminated body>

Next, the structure of the laminate of one embodiment of the present invention will be described with reference to the drawings.

1 to 3 are cross-sectional schematic diagrams of laminates showing configurations of the laminates of the first to third aspects of the present invention. In the laminates of the first to third aspects of the present invention described below, the adhesive surface of the pressure-sensitive adhesive layer (X) (or the second pressure-sensitive adhesive layer (X2)) to be attached to the support (that is, on the opposite side to the support) surface) and the surface of the energy ray-curable resin layer (I) on the opposite side to the support layer (II) side, it is good also as a structure in which a release material was further laminated.

[Laminate of first aspect]

As a laminate of the first aspect of the present invention, laminates 1a and 1b shown in FIG. 1 are exemplified.

The laminates 1a and 1b include an energy ray-curable resin layer (I), a base material (Y), and a support layer (II) having an adhesive layer (X), and the base material (Y) and the energy ray-curable resin layer ( I) has a direct laminated configuration;

In the laminate of the first aspect of the present invention, the adhesive surface of the pressure-sensitive adhesive layer (X) is attached to a support (not shown).

The support layer (II) contains thermally expandable particles in at least one layer, and in the layered product (1a), the base material (Y) is a base material having a single-layer structure composed only of the expandable base layer (Y1) containing the thermally expandable particles. am.

The substrate (Y) may be a single-layer substrate composed of only the expandable substrate layer (Y1), as in the laminate (1a) shown in FIG. 1 (a), or as in the laminate (1b) shown in FIG. 1 (b). , it may be a multi-layered substrate having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2). When the base material (Y) has an intumescent base layer (Y1) and a non-expandable base layer (Y2), the base material (Y) may consist only of the intumescent base layer (Y1) and the non-expandable base layer (Y2).

In addition, it is preferable that the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) have a structure in which they are directly laminated.

In the layered product 1a shown in Fig. 1(a), thermally expandable particles contained in the expandable base material layer (Y1) expand by thermal expansion treatment, resulting in unevenness on the surface of the base material (Y), and energy ray curing properties. The contact area with the cured resin layer (I') formed by previously curing the resin layer (I) is reduced.

At this time, the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X) is adhered to an unillustrated support. Even if the pressure-sensitive adhesive layer (X) is adhered so as to sufficiently adhere to the support, even if a force generating irregularities is generated on the surface of the pressure-sensitive adhesive layer (X) side of the expandable base material layer (Y1), the force of repelling from the pressure-sensitive adhesive layer (X) it is easy to occur Therefore, unevenness is difficult to form on the surface of the base material (Y) on the pressure-sensitive adhesive layer (X) side.

As a result, the layered product 1a can be collectively and easily separated with a slight force at the interface P between the base material Y of the support layer (II) and the cured resin layer (I').

Furthermore, by forming the adhesive layer (X) of the layered product 1a from an adhesive composition having a high adhesive force to the support, it is also possible to make the separation more easily possible at the interface P.

In addition, from the viewpoint of suppressing transmission of stress due to thermally expandable particles to the pressure-sensitive adhesive layer (X) side, as in the laminate 1b shown in FIG. ) and a non-expandable substrate layer (Y2).

Since the stress due to the expansion of the thermally expandable particles of the expandable substrate layer (Y1) is suppressed by the non-expandable substrate layer (Y2), it is difficult to transmit to the pressure-sensitive adhesive layer (X).

Therefore, irregularities hardly occur on the surface of the support side of the pressure-sensitive adhesive layer (X), and the adhesion between the pressure-sensitive adhesive layer (X) and the support hardly changes before and after the thermal expansion treatment, and good adhesion can be maintained. As a result, irregularities are easily formed on the surface of the expandable base layer (Y1) on the energy ray-curable resin layer (I) side, and as a result, the At the interface P, it becomes easily separable collectively with a slight force.

In addition, as in the laminate (1b) shown in FIG. 1(b), the expandable base layer (Y1) and the energy ray-curable resin layer (I) are directly laminated, and the expandable base layer (Y1) of the non-expandable base layer (Y2) It is preferable that it is a structure in which adhesive layer (X) was laminated|stacked on the surface on the opposite side to ).

[Laminate of the second aspect]

As a laminate of the second aspect of the present invention, laminates 2a and 2b shown in FIG. 2 are exemplified.

In the laminates 2a and 2b, the pressure-sensitive adhesive layer (X) of the support layer (II) includes the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), and the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X1) The base material (Y) is held by the pressure-sensitive adhesive layer (X2), and the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (X1) is directly laminated with the energy ray-curable resin layer (I).

In the laminate of the second aspect of the present invention, the adhesive surface of the second pressure-sensitive adhesive layer (X2) is attached to a support (not shown).

Also in the laminate of the second aspect of the present invention, it is preferable that the base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles.

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

However, as described above, as shown in FIG. 2(b), from the viewpoint of forming a laminate that maintains good adhesion between the second pressure-sensitive adhesive layer (X2) and the support before and after the thermal expansion treatment, the substrate (Y) It is preferable to have an expandable base layer (Y1) and a non-expandable base layer (Y2).

Further, in the laminate of the second aspect, when using a substrate (Y) having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), as shown in FIG. 2(b), the expandable substrate layer ( Y1), on the surface of the energy ray curable resin layer (I) side, the first pressure-sensitive adhesive layer (X1) is laminated, and on the surface of the non-expandable base layer (Y2) on the opposite side to the expandable base layer (Y1), It is preferable to have a structure in which two pressure-sensitive adhesive layers (X2) are laminated.

In the laminate of the second aspect, thermally expandable particles in the expandable base material layer (Y1) constituting the base material (Y) expand through thermal expansion treatment, and irregularities are formed on the surface of the expandable base layer (Y1).

Then, the irregularities formed on the surface of the expandable substrate layer (Y1) also push the first pressure-sensitive adhesive layer (X1) upward, and the irregularities are also formed on the adhesive surface of the first pressure-sensitive adhesive layer (X1), so that the first pressure-sensitive adhesive layer (X1) and the contact area with the cured resin layer (I') formed by previously curing the energy ray-curable resin layer (I) is reduced. As a result, at the interface (P) between the first pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I'), it can be easily separated collectively with a slight force.

Further, in the laminate of the second aspect of the present invention, the expandable base layer of the base material (Y) included in the support layer (II) from the viewpoint of making the laminate easily separable collectively with a little force at the interface (P). (Y1) and the first pressure-sensitive adhesive layer (X1) are preferably laminated directly.

[Laminate of the third aspect]

As a laminate of the third aspect of the present invention, the laminate 3 shown in FIG. 3 is exemplified.

The layered product 3 shown in FIG. 3 has a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, on one surface side of a base material (Y), and the other surface of the base material (Y). On the side, a support layer (II) having a second pressure-sensitive adhesive layer (X2) as a non-expandable pressure-sensitive adhesive layer is provided, and the first pressure-sensitive adhesive layer (X1) and the energy ray-curable resin layer (I) are directly laminated.

In the layered product 3, the adhesive surface of the second pressure sensitive adhesive layer X2 is attached to a support (not shown).

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

In the laminate of the third aspect of the present invention, thermally expandable particles in the first pressure-sensitive adhesive layer (X1), which are expandable pressure-sensitive adhesive layers, expand by thermal expansion treatment, and irregularities are formed on the surface of the first pressure-sensitive adhesive layer (X1). The contact area between the first pressure-sensitive adhesive layer (X1) and the cured resin layer (I') obtained by previously curing the energy ray-curable resin layer (I) is reduced.

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

Therefore, irregularities are easily formed on the surface of the energy ray-curable resin layer (I) side of the first pressure-sensitive adhesive layer (X1) by the thermal expansion treatment, and as a result, the first pressure-sensitive adhesive layer (X1) of the support layer (II) At the interface (P) of the overcured resin layer (I'), it becomes easily removable all at once with a slight force.

The laminate of one aspect of the present invention may consist only of the support layer (II) and the energy ray-curable resin layer (I), or have layers other than the support layer (II) and the energy ray-curable resin layer (I). It can be done. As an example of another layer, the adhesive layer etc. which are formed on the surface opposite to the support layer (II) of energy ray-curable resin layer (I) are mentioned, for example.

Further, the laminate of one embodiment of the present invention preferably does not include a thermosetting resin layer from the viewpoint of requiring no heating as much as possible in steps other than the heat expansion treatment. However, the thermosetting resin layer here means a layer that has thermosetting properties and is non-energy ray curable.

<Various physical properties of the laminate>

(peel force (F ₀ ))

Before curing of the energy ray-curable resin layer (I) and before the thermal expansion treatment, from the viewpoint of sufficiently fixing the object to be sealed and not adversely affecting the sealing operation, the support layer (II) and the energy ray-curable resin layer (I) It is preferable that adhesiveness is high.

From the above viewpoint, in the laminate of one aspect of the present invention, the support layer (II) and the energy ray-curable resin layer (I) before the energy ray-curable resin layer (I) is cured and before the thermal expansion treatment is performed. The peel force (F ₀ ) at the time of separation at the interface P of is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, still more preferably 160 mN/25 mm or more And, preferably, it is 50000 mN/25 mm or less.

In addition, peel force (F ₀ ) is a value measured by the following measuring method.

<Measurement of peel force (F ₀ )>

After the laminate is left still for 24 hours in an environment of 23° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Co., Ltd., product name “PL Shin”) is affixed to the surface of the energy ray curable resin layer (I). .

Next, the support layer (II) side of the laminate is affixed to a glass plate (produced by Yuko Co., Ltd., float plate glass, 3 mm (JIS R 3202 product)) through an adhesive. Next, the edge of the glass plate to which the laminate was attached is fixed to the lower chuck of a universal tensile tester (manufactured by Orientec Co., Ltd., product name "Tensilon UTM-4-100").

Subsequently, the adhesive tape and the support layer (II) are fixed with the upper chuck of the universal tensile tester so as to peel at the interface (P) between the support layer (II) and the energy ray-curable resin layer (I) of the laminate. Then, under the same environment as above, based on JIS Z 0237: 2000, the peeling force measured when peeling from the interface P at a tensile speed of 300 mm/min by the 180° peeling method was defined as "peel force (F ₀ )”.

(peel force (F ₁ ))

In the laminate of one aspect of the present invention, after the energy ray-curable resin layer (I) is cured to form the cured resin layer (I'), the support layer (II) and the cured resin layer (I') are subjected to heat expansion treatment. ), the peeling force (F ₁ ) at the time of separation at the interface P is usually 2000 mN/25 mm or less, preferably from the viewpoint of enabling easy separation at the interface P with a slight force. is 1000 mN/25 mm or less, more preferably 500 mN/25 mm or less, more preferably 150 mN/25 mm or less, even more preferably 100 mN/25 mm or less, still more preferably 50 mN/25 mm or less or less, most preferably 0 mN/25 mm.

In the case where the peel force (F ₁ ) is 0 mN/25 mm, even if the peel force is to be measured, the peel force is too small and thus the measurement becomes impossible.

In addition, peel force (F ₁ ) is a value measured by the following measuring method.

<Measurement of Peel Force (F ₁ )>

After the laminate was left still for 24 hours in an environment of 23°C and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name "PL Shin") was applied to the surface of the energy ray curable resin layer (I) of the laminate. attach to

Next, the support layer (II) side of the laminate is affixed to a glass plate (produced by Yuko Co., Ltd., float plate glass, 3 mm (JIS R 3202 product)) through an adhesive.

Subsequently, ultraviolet rays are irradiated three times under conditions of an illuminance of 215 mW/cm 2 and an amount of light of 187 mJ/cm 2 to cure the energy ray-curable resin layer (I) to form a cured resin layer (I'). And the glass plate and the laminate are heated at the maximum expansion temperature for 3 minutes to expand the thermally expandable particles in the expandable substrate layer (Y1) of the laminate. After that, it was carried out in the same way as the measurement of the peeling force (F ₀ ) described above, and the peeling force measured when peeling at the interface P between the support layer (II) and the cured resin layer (I′) under the above conditions Let it be “peel force (F ₁ )”.

Further, in the measurement of the peel force (F ₁ ), when trying to fix the support layer (II) of the laminate with the upper chuck of the universal tensile tester, the cured resin layer (I') is completely at the interface (P) If it is separated and cannot be fixed, the measurement is terminated, and the peeling force (F ₁ ) at that time is set to “0 mN/25 mm”.

(Adhesive strength of pressure-sensitive adhesive layer (X))

In the laminate of one aspect of the present invention, the adhesive strength of the pressure-sensitive adhesive layer (X) (first pressure-sensitive adhesive layer (X1) and second pressure-sensitive adhesive layer (X2)) of the support layer (II) at room temperature (23 ° C.) It 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, still more preferably 0.5 to 4.0 N/25 mm. .

When the support layer (II) has the first pressure sensitive adhesive layer (X1) and the second pressure sensitive adhesive layer (X2), the adhesive strength of the first pressure sensitive adhesive layer (X1) and the second pressure sensitive adhesive layer (X2) is preferably within the above range, respectively. , From the viewpoint of improving the adhesion to the support and enabling easier separation at the interface (P), the adhesive strength of the support and the second pressure-sensitive adhesive layer (X2) to be attached is the adhesive force of the first pressure-sensitive adhesive layer (X1). Higher is more preferable.

(Adhesion of energy ray-curable resin layer (I))

In the laminate of one aspect of the present invention, from the viewpoint of improving adhesion with the object to be sealed, the energy ray-curable resin layer (I) is the surface on which the object to be sealed is placed (ie, the side opposite to the support layer (II)) surface) has adhesiveness.

Specifically, the adhesive strength of the surface of the energy ray-curable resin layer (I) on the side where the object to be sealed is mounted at room temperature (23°C) is preferably 0.05 N/25 from the viewpoint of sufficiently fixing the object to be sealed. mm or more, more preferably 0.10 N/25 mm or more, still more preferably 0.50 N/25 mm or more. The upper limit of the adhesive strength of the surface is not particularly limited, but is usually 50 N/25 mm or less, may be 40 N/25 mm or less, or may be 30 N/25 mm or less.

In addition, in this specification, these adhesive forces are values measured by the following measuring method.

<Measurement of adhesive force>

On the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) formed on the release film, a 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) is laminated.

Then, the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) was affixed to a stainless steel plate (SUS304 polished No. 360), which is an adherend, for 24 hours in an environment of 23°C and 50% RH (relative humidity). After leaving still, the adhesive strength at 23°C is measured at a tensile rate of 300 mm/min by the 180° peeling method based on JIS Z 0237:2000 under the same environment.

(probe tack value of substrate (Y))

The substrate (Y) included in the support layer (II) is a non-adhesive substrate.

In one aspect of the present invention, determination of whether or not the substrate is non-adhesive is determined based on JIS Z 0237: 1991 with respect to the surface of the target substrate. If the probe tack value is less than 50 mN / 5 mmφ, The base material is judged as a "non-adhesive base material". On the other hand, if the probe tack value is 50 mN/5 mmφ or more, the substrate is judged to be an "adhesive substrate".

The probe tack value on the surface of the base material (Y) of the support layer (II) used in one aspect of the present invention is usually less than 50 mN/5 mmφ, but preferably less than 30 mN/5 mmφ, and more It is preferably less than 10 mN/5 mmφ, more preferably less than 5 mN/5 mmφ.

The probe tack value on the surface of the substrate (Y) is a value measured by the following measuring method.

<Measurement of probe tack value>

After cutting the substrate to be measured into a square of 10 mm on each side, what was left still in an environment of 23°C and 50% RH (relative humidity) for 24 hours was used as a test sample. In an environment of 23°C and 50% RH (relative humidity), the probe tack value on the surface of the test sample was measured using a tacking tester (manufactured by Nippon Special Instrument Co., Ltd., product name "NTS-4800") according to JIS Z 0237: Measured in accordance with 1991. Specifically, a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N/cm for 1 second, and then the probe is separated from the surface of the test sample at a rate of 10 mm/sec. Measure the force required to perform the test, and use the obtained value as the probe tack value of the test sample.

Next, each layer constituting the laminate of one embodiment of the present invention will be described.

<Support Layer (II)>

The support layer (II) of the laminate of one embodiment of the present invention has a base material (Y) and an adhesive layer (X), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (X) contains thermally expandable particles. . As described above, the supporting layer (II) is a layer that is separated from the energy ray-curable resin layer (I), which is the object to be supported, by heat expansion treatment, and serves as a so-called temporarily fixed layer.

In the case where the layer containing thermally expandable particles is included in the structure of the base material (Y) and the case where it is included in the structure of the pressure-sensitive adhesive layer (X), the support layer (II) used in one aspect of the present invention is the following Divided into aspects.

• Support layer (II) of the first aspect: Support layer (II) provided with a substrate (Y) having an expandable substrate layer (Y1) containing thermally expandable particles.

Support layer (II) of the second aspect: a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, and a second pressure-sensitive adhesive layer (X2), which is a non-expandable pressure-sensitive adhesive layer, on both sides of the substrate (Y) (II) a support layer having a.

[Support layer (II) of the first aspect]

As the support layer (II) of the first aspect, as shown in FIGS. 1 and 2 , those in which the base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles are exemplified.

In the support layer (II) of the first aspect, it is preferable that the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer from the viewpoint of enabling easy separation at the interface (P) collectively with a slight force.

Specifically, in the support layer (II) included in the laminates 1a and 1b shown in Fig. 1, it is preferable that the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer.

Moreover, in the support layer (II) which the laminates 2a and 2b shown in FIG. 2 have, it is preferable that both the 1st adhesive layer (X1) and the 2nd adhesive layer (X2) are non-expandable adhesive layers.

Like the support layer (II) of the first aspect, when the base material (Y) has the expandable base layer (Y1), the pressure-sensitive adhesive layer (X) does not need to have expandability, and the composition, configuration and process for imparting expandability not bound As a result, when designing the pressure-sensitive adhesive layer (X), for example, since it is possible to give priority to desired performance other than expansibility, such as performance such as adhesiveness, productivity, and economy, the design freedom of the pressure-sensitive adhesive layer (X) is improved. can make it

The thickness of the substrate (Y) before the thermal expansion treatment of the support layer (II) of the first aspect is preferably 10 to 1000 μm, more preferably 20 to 700 μm, still more preferably 25 to 500 μm, still more preferably is 30 to 300 μm.

The thickness of the pressure-sensitive adhesive layer (X) before the thermal expansion treatment of the support layer (II) of the first aspect is preferably 1 to 60 μm, more preferably 2 to 50 μm, still more preferably 3 to 40 μm, still more preferably It is preferably 5 to 30 μm.

In addition, in this specification, for example, as shown in FIG. 2, when support layer (II) has a some adhesive layer (X), said "thickness of adhesive layer (X)" is each The thickness of the pressure-sensitive adhesive layer (in Fig. 2, the thickness of each of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2)) is meant.

In addition, in this specification, the thickness of each layer which comprises a laminated body means the value measured by the method described in the Example.

In the support layer (II) of the first aspect, the thickness ratio [(Y1)/(X)] of the expandable substrate layer (Y1) and the pressure-sensitive adhesive layer (X) before the thermal expansion treatment is preferably 1000 or less, and It is preferably 200 or less, more preferably 60 or less, and still more preferably 30 or less.

If the thickness ratio is 1000 or less, the laminate can be easily separated with a slight force at the interface P between the support layer (II) and the cured resin layer (I') by thermal expansion treatment.

In addition, the thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, still more preferably 5.0 or more.

In addition, in the support layer (II) of the first aspect, the base material (Y) may be composed only of the expandable base layer (Y1) as shown in Fig. 1 (a), or as shown in Fig. 1 (b), It may have an expandable base layer (Y1) on the energy ray-curable resin layer (I) side and a non-expandable base layer (Y2) on the pressure-sensitive adhesive layer (X) side.

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

[Support layer (II) of the second aspect]

As the support layer (II) of the second aspect, as shown in Fig. 3, the first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, on both sides of the base material (Y), respectively, and non-expandable What has the 2nd adhesive layer (X2) which is an adhesive layer is mentioned.

In addition, in the support layer (II) of the second aspect, the first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer, and the energy ray-curable resin layer (I) are in direct contact.

In the support layer (II) of the second aspect, the substrate (Y) is preferably a non-expandable substrate. It is preferable that the non-expandable substrate is composed of only the non-expandable substrate layer (Y2).

In the support layer (II) of the second aspect, the thickness ratio of the first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer, and the second pressure-sensitive adhesive layer (X2), which is a non-expandable pressure-sensitive adhesive layer, before thermal expansion treatment [(X1)/ (X2)] is preferably from 0.1 to 80, more preferably from 0.3 to 50, still more preferably from 0.5 to 15.

In addition, in the support layer (II) of the second aspect, the thickness ratio of the first pressure-sensitive adhesive layer (X1), which is the expandable pressure-sensitive adhesive layer before heat expansion treatment, and the base material (Y) [(X1) / (Y)], It is preferably 0.05 to 20, more preferably 0.1 to 10, still more preferably 0.2 to 3.

Hereinafter, after explaining the thermally expandable particles contained in any layer constituting the support layer (II), the expandable substrate layer (Y1), the non-expandable substrate layer (Y2), and the pressure-sensitive adhesive layer (X) constituting the substrate (Y) describe in detail about

[Thermally expansible particles]

The thermally expandable particles used in one aspect of the present invention may be particles that expand by a predetermined thermal expansion treatment.

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

In addition, the average particle diameter of thermally expandable particles before expansion is the volume median particle diameter (D ₅₀ ), which is measured using a laser diffraction type particle size distribution analyzer (for example, manufactured by Malvern, product name “Mastersizer 3000”). , In the particle distribution of the thermally expandable particles before expansion, it means the particle size corresponding to 50% of the cumulative volume frequency calculated starting with the particle size of the thermally expandable particles before expansion.

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

In addition, the 90% particle diameter (D ₉₀ ) of the thermally expandable particles before expansion is the heat before expansion, measured using a laser diffraction type particle size distribution analyzer (eg, manufactured by Malvern, product name “Mastersizer 3000”). In the particle distribution of expandable particles, it means a particle size corresponding to a cumulative volume frequency calculated from the smaller particle size of the thermally expandable particles before expansion to 90%.

The thermally expansible particles used in one aspect of the present invention may be particles having an expansion start temperature (t) higher than the curing temperature of the encapsulant and which do not expand when the encapsulant is cured. Specifically, the expansion initiation temperature (t ) is preferably a thermally expandable particle adjusted to 60 to 270°C. In addition, the expansion start temperature (t) is appropriately selected according to the curing temperature of the sealing material to be used.

In addition, in this specification, the expansion start temperature (t) of thermally expandable particle|grains means the value measured based on the method described in the Example.

The thermally expansible particles are preferably a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an encapsulated component that is enclosed in the outer shell and vaporizes when heated to a predetermined temperature.

As the thermoplastic resin constituting the outer shell of the microencapsulation foaming agent, for example, vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polychlorinated Vinylidene, polysulfone, etc. are mentioned.

Examples of the encapsulated component included in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclo Propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane , octadecane, nanodecane, isotridecane, 4-methyldodecane, isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane , isooctadecane, isonanodecane, 2,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, penta Decyl cyclohexane, hexadecyl cyclohexane, heptadecyl cyclohexane, octadecyl cyclohexane, etc. are mentioned.

These encapsulation components may be used independently or may use 2 or more types together.

The expansion start temperature t of the thermally expandable particles can be adjusted by appropriately selecting the type of the encapsulated component.

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

<Expandable base layer (Y1)>

The expandable substrate layer (Y1) included in the support layer (II) used in one aspect of the present invention is a layer that contains thermally expandable particles and can be expanded by a predetermined thermal expansion treatment.

In addition, from the viewpoint of improving interlayer adhesion between the expandable base layer (Y1) and other layers to be laminated, the surface of the expandable base layer (Y1) is subjected to surface treatment by an oxidation method, a roughening method, or the like, an adhesion-facilitating treatment, or a primer treatment. may be carried out.

Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of the roughening method include sandblasting, A solvent treatment method etc. are mentioned.

In one aspect of the present invention, it is preferable that the expandable substrate layer (Y1) satisfies the following requirement (1).

Requirement (1): The storage elastic modulus (E'(t)) of the expandable substrate layer (Y1) at the expansion start temperature (t) of the thermally expandable particles is 1.0 × 10 ⁷ Pa or less.

In addition, in this specification, the storage elastic modulus (E') of the expandable substrate layer (Y1) at a predetermined temperature means a value measured by the method described in Examples.

The above requirement (1) can be said to be an index indicating the rigidity of the expandable substrate layer (Y1) immediately before expansion of the thermally expandable particles.

In order to enable easy separation with a slight force at the interface (P) between the support layer (II) and the cured resin layer (I'), when heated to a temperature equal to or higher than the expansion start temperature (t), the energy ray of the support layer (II) It is necessary to facilitate the formation of irregularities on the surface of the curable resin layer (I) and the laminated side.

In short, the expandable substrate layer (Y1) satisfying the above requirement (1) is sufficiently large as the thermally expandable particles expand at the expansion start temperature (t), and the support layer on which the energy ray-curable resin layer (I) is laminated ( It becomes easy to form irregularities on the surface of II).

As a result, a laminate can be easily separated with a slight force at the interface P between the support layer (II) and the cured resin layer (I').

The storage elastic modulus (E'(t)) of the expandable substrate layer (Y1) specified in the requirement (1) is, from the above viewpoint, preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 × 10 ⁶ Pa or less. , more preferably 6.0 × 10 ⁶ Pa or less, still more preferably 4.0 × 10 ⁶ Pa or less.

In addition, the flow of the expanded thermally expandable particles is suppressed, the shape retention of the irregularities formed on the surface of the support layer (II) on the side where the energy ray-curable resin layer (I) is laminated is improved, and the interface (P) slightly The storage modulus (E'(t)) of the expandable substrate layer (Y1), which is specified in requirement (1), is preferably 1.0 × 10 ³ Pa or more, from the viewpoint of making the separation more easily possible with the force of It is preferably 1.0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

The expandable substrate layer (Y1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.

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

Examples of additives for substrates include light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, colorants and the like.

In addition, these additives for base materials may be used independently, respectively, and may use 2 or more types together.

When these additives for substrates are contained, the content of each additive for substrates is preferably from 0.0001 to 20 parts by mass, more preferably from 0.001 to 10 parts by mass with respect to 100 parts by mass of the resin.

The content of the thermally expandable particles is preferably 1 to 40% by mass, based on the total amount (100% by mass) of the expandable substrate layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y); More preferably, it is 5 to 35 mass%, still more preferably 10 to 30 mass%, still more preferably 15 to 25 mass%.

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

In short, even if the resin contained in the resin composition (y) is an adhesive resin, in the process of forming the expandable substrate layer (Y1) from the resin composition (y), the adhesive resin is polymerized with a polymerizable compound, and the resulting resin is It is sufficient if it becomes a non-adhesive resin and the expandable base material layer (Y1) containing this resin becomes non-adhesive.

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

Moreover, when the said resin is a copolymer which has 2 or more types of structural units, the form of this copolymer is not specifically limited, Any of a block copolymer, a random copolymer, and a graft copolymer may be sufficient.

The content of the resin is preferably 50 to 99% by mass, relative to the total amount (100% by mass) of the expandable substrate layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y). It is preferably 60 to 95% by mass, more preferably 65 to 90% by mass, still more preferably 70 to 85% by mass.

In addition, from the viewpoint of forming the expandable substrate layer (Y1) satisfying the above requirement (1), the resin contained in the resin composition (y) contains at least one selected from acrylic urethane resins and olefin resins. It is desirable to do

Moreover, as said acrylurethane type-resin, the following resin (U1) is preferable.

- An acrylic urethane-based resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing (meth)acrylic acid ester.

(Acrylic urethane resin (U1))

Examples of the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and polyvalent isocyanate.

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

Examples of the polyol used as a raw material of the urethane prepolymer (UP) include alkylene type polyols, ether type polyols, ester type polyols, esteramide type polyols, ester/ether type polyols, and carbonate type polyols.

These polyols may be used independently or may use 2 or more types together.

The polyol used in one aspect of the present invention is preferably a diol, more preferably an ester type diol, an alkylene type diol and a carbonate type diol, and still more preferably an ester type diol and a carbonate type diol.

Examples of the ester type diol include alkanediol such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Alkylene glycol, such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; 1 type or 2 or more types selected from diols, such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyl dicarboxylic acid, diphenylmethane-4,4'-dicar Boxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, hetic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid and dicarboxylic acids such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and methylhexahydrophthalic acid, and condensation polymers with one or two or more kinds selected from anhydrides thereof.

Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, Polybutylene hexamethylene adipate diol, poly diethylene adipate diol, poly(polytetramethylene ether) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, poly Butylene azelate diol, polybutylene sebacate diol, polyneopentyl terephthalate diol, etc. are mentioned.

Examples of the alkylene-type diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; Alkylene glycol, such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; Polyalkylene glycol, such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; etc. can be mentioned.

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

Examples of the polyvalent isocyanate used as a raw material of the urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

These polyhydric isocyanates may be used independently or may use 2 or more types together.

Moreover, these polyhydric isocyanates may be trimethylolpropane adduct-type modified products, biuret-type modified products made to react with water, and isocyanurate-type modified products containing an isocyanurate ring.

Among these, diisocyanate is preferable as the polyvalent isocyanate used in one aspect of the present invention, and 4,4'-diphenylmethane diisocyanate (MDI) and 2,4-tolylene diisocyanate (2,4-TDI) , 2,6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and at least one selected from alicyclic diisocyanates are more preferred.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, and 1,3-cyclohexane. Although diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc. are mentioned, isophorone diisocyanate (IPDI) is preferable.

In one aspect of the present invention, the urethane prepolymer (UP) serving as the main chain of the acrylic urethane resin (U1) is preferably a linear urethane prepolymer that is a reaction product of a diol and diisocyanate and has ethylenically unsaturated groups at both ends.

As a method for introducing ethylenically unsaturated groups into both terminals of the linear urethane prepolymer, a method in which a diol and a diisocyanate compound are reacted with an NCO group at the terminal of the linear urethane prepolymer formed by reacting a hydroxyalkyl (meth)acrylate can be heard

As hydroxyalkyl (meth)acrylate, for example, 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. are mentioned.

As a vinyl compound used as the side chain of acrylic urethane type-resin (U1), at least (meth)acrylic acid ester is contained.

As the (meth)acrylic acid ester, at least one selected from alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates is preferable, and alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates are used in combination. It is more preferable to

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

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

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

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

These may be used independently and may use 2 or more types together.

The content of the (meth)acrylic acid ester in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably based on the total amount (100% by mass) of the vinyl compound. It is 80-100 mass %, More preferably, it is 90-100 mass %.

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

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

(olefin resin)

Preferred olefinic resins as resins contained in the resin composition (y) are polymers having at least structural units derived from olefin monomers.

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

Among these, ethylene and propylene are preferred.

As specific olefin-based resins, for example, ultra-low density polyethylene (VLDPE, density: 880 kg/m3 or more and less than 910 kg/m3), low density polyethylene (LDPE, density: 910 kg/m3 or more and less than 915 kg/m3), polyethylene resins such as medium-density polyethylene (MDPE, density: 915 kg/m 3 or more and less than 942 kg/m 3 ), high-density polyethylene (HDPE, density: 942 kg/m 3 or more), and linear low-density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymers; Olefin type elastomer (TPO); poly(4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); ethylene-vinyl alcohol copolymer (EVOH); olefinic terpolymers such as ethylene-propylene-(5-ethylidene-2-norbornene); etc. can be mentioned.

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

For example, as an acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin, a modified polymer formed by graft polymerization of an unsaturated carboxylic acid or an anhydride thereof to the unmodified olefin-based resin described above is mentioned. can

Examples of the unsaturated carboxylic acids or anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, and anhydride. Itaconic acid, glutaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride, norbornenedicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, etc. are mentioned.

In addition, unsaturated carboxylic acid or its anhydride may be used independently, and may use 2 or more types together.

As the acrylic-modified olefin-based resin formed by performing acrylic modification on the olefin-based resin, a modified polymer formed by graft polymerization of an alkyl (meth)acrylate as a side chain to the above-mentioned unmodified olefin-based resin as a main chain can be heard

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

As said alkyl (meth)acrylate, the same thing as the compound which can be selected as a monomer (a1') mentioned later is mentioned, for example.

Examples of the hydroxyl-modified olefin-based resin obtained by subjecting the olefin-based resin to hydroxyl-modification include a modified polymer obtained by graft-polymerizing a hydroxyl-containing compound onto the above-described unmodified olefin-based resin as a main chain.

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

(Resin other than acrylic urethane resin and olefin resin)

1 aspect of this invention WHEREIN: You may contain resin other than acrylic urethane type resin and olefin type resin in the range which does not impair the effect of this invention in the resin composition (y).

Examples of such resin include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; Acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; Polyurethane that does not correspond to acrylic urethane-based resins; polysulfone; polyether ether ketone; polyethersulfone; polyphenylene sulfide; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resin; acrylic resin; A fluorine-type resin etc. are mentioned.

However, from the viewpoint of forming the expandable substrate layer (Y1) satisfying the above requirement (1), the content ratio of resins other than the acrylic urethane-based resin and the olefin-based resin in the resin composition (y) is preferably smaller.

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

(Non-solvent type resin composition (y1))

As the resin composition (y) used in one aspect of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50000 or less, an energy ray polymerizable monomer, and the above-mentioned thermally expandable particles are blended. and a non-solvent type resin composition (y1) in which no solvent is incorporated.

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

By irradiating energy rays to the coating film formed from the non-solvent type resin composition (y1), it is easy to form the expandable substrate layer (Y1) that satisfies the above requirement (1).

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

The mass average molecular weight (Mw) of the oligomer contained in the non-solvent type resin composition (y1) is 50000 or less, but is preferably 1000 to 50000, more preferably 2000 to 40000, still more preferably 3000 to 35000, still more preferably It is 4000 to 30000 at most.

Moreover, as said oligomer, among resins contained in the resin composition (y) mentioned above, a mass average molecular weight should just have 50000 or less ethylenically unsaturated group, but the above-mentioned urethane prepolymer (UP) is preferable.

Moreover, as the said oligomer, the modified olefin resin which has an ethylenically unsaturated group can also be used.

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

Examples of the energy ray polymerizable monomer include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxy (meth)acrylate. , alicyclic polymerizable compounds such as cyclohexyl (meth)acrylate, adamantane (meth)acrylate, and tricyclodecane acrylate; aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate, and phenolethylene oxide-modified acrylate; and heterocyclic polymerizable compounds such as tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, and N-vinylcaprolactam.

These energy ray polymerizable monomers may be used independently or may use 2 or more types together.

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

1 aspect of this invention WHEREIN: It is preferable that a non-solvent type resin composition (y1) further mix|blends a photoinitiator.

By containing a photoinitiator, hardening reaction can fully advance also by irradiation of a comparatively low-energy energy ray.

As the photopolymerization initiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthiurammono Sulfide, azobisisobutyrol nitrile, dibenzyl, diacetyl, 8-chloroanthraquinone, etc. are mentioned.

These photoinitiators may be used independently or may use 2 or more types together.

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

<Non-expandable base layer (Y2)>

Examples of the material for forming the non-expandable substrate layer (Y2) constituting the substrate (Y) include paper materials, resins, metals, and the like, and can be appropriately selected depending on the use of the laminate of one embodiment of the present invention. there is.

As the paper material, for example, thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfated paper, glassine paper and the like are exemplified.

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

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

These forming materials may be comprised by 1 type, and may use 2 or more types together.

Examples of the non-expandable substrate layer (Y2) in which two or more types of forming materials are used in combination include those in which a paper material is laminated with a thermoplastic resin such as polyethylene, and those in which a metal film is formed on the surface of a resin film or sheet containing a resin. can

In addition, as a method of forming a metal layer, for example, a method of depositing the metal by a PVD method such as vacuum deposition, sputtering, or ion plating, or a method of attaching a metal foil made of the metal using a general adhesive etc. can be mentioned.

Here, in one aspect of the present invention, when the expandable particles included in the expandable base layer (Y1) expand, the formation of irregularities on the surface of the expandable base layer (Y1) on the non-expandable base layer (Y2) side is suppressed. And, from the viewpoint of preferentially forming irregularities on the surface of the pressure-sensitive adhesive layer (X1) side of the expandable base layer (Y1), the non-expandable base layer (Y2) has a rigidity to the extent that it is not deformed by expansion of the expandable particles. It is desirable to have. Specifically, it is preferable that the storage elastic modulus (E'(t)) of the non-expandable substrate layer (Y2) at the temperature (t) at the start of expansion of the expandable particles is 1.1 × 10 ⁷ Pa or more.

Further, from the viewpoint of improving interlayer adhesion between the non-expandable base layer (Y2) and other layers to be laminated, when the non-expandable base layer (Y2) contains a resin, also for the surface of the non-expandable base layer (Y2), Similar to the above-described expandable substrate layer (Y1), surface treatment by an oxidation method, a roughening method, or the like, an adhesion-facilitating treatment, or a primer treatment may be performed.

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

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

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

In addition, the non-expandable substrate layer (Y2) may contain thermally 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 substrate layer (Y2), it is possible to adjust the volume change rate within the above range even if the thermally expandable particles are contained.

However, it is preferable that the non-expandable substrate layer (Y2) does not contain thermally expandable particles. When the non-expandable substrate layer (Y2) contains thermally expandable particles, the smaller the content, the better. , it is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass.

<Adhesive layer (X)>

The adhesive layer (X) included in the support layer (II) used in one aspect of the present invention can be formed from an adhesive composition (x) containing an adhesive resin.

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

Hereinafter, each component contained in the pressure-sensitive adhesive composition (x) is described.

In addition, even when the support layer (II) has the first pressure sensitive adhesive layer (X1) and the second pressure sensitive adhesive layer (X2), the first pressure sensitive adhesive layer (X1) and the second pressure sensitive adhesive layer (X2) are also each shown below. It can be formed from the pressure-sensitive adhesive composition (x) containing the component.

(adhesive resin)

As the adhesive resin used in one aspect of the present invention, it is preferable that the resin alone has adhesiveness and is a polymer having a mass average molecular weight (Mw) of 10,000 or more.

The mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention is preferably from 10,000 to 2,000,000, more preferably from 20,000 to 1,500,000, still more preferably from the viewpoint of improving the adhesive strength. 30,000 to 1,000,000.

Examples of specific adhesive resins include rubber-based resins such as acrylic resins, urethane-based resins and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based resins.

These adhesive resins may be used independently or may use 2 or more types together.

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

1 aspect of this invention WHEREIN: It is preferable that adhesive resin contains acrylic resin from a viewpoint of expressing excellent adhesive force.

In the case of using the support layer (II) having the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), the acrylic resin is applied to the first pressure-sensitive adhesive layer (X1) in contact with the energy ray-curable resin layer (I). By being included, it is possible to easily form irregularities on the surface of the first pressure-sensitive adhesive layer (X1).

The content ratio of the acrylic resin in the adhesive resin is preferably 30 to 100% by mass, more preferably 30 to 100% by mass relative to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X) is 50 to 100% by mass, 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 ingredient of the PSA composition (x) or the total amount (100% by mass) of the PSA layer (X). It is preferably 50 to 100% by mass, more preferably 60 to 98% by mass, still more preferably 70 to 95% by mass.

(crosslinking agent)

1 aspect of this invention WHEREIN: When the adhesive composition (x) contains the adhesive resin which has a functional group, it is preferable to contain a crosslinking agent further.

The said crosslinking agent reacts with the adhesive resin which has a functional group, and crosslinks the adhesive resin with the said functional group as a crosslinking origin.

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

These crosslinking agents may be used independently or may use 2 or more types together.

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

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

(tackifier)

1 aspect of this invention WHEREIN: The adhesive composition (x) may further contain a tackifier from a viewpoint of improving adhesive force more.

In this specification, "tackifier" refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000 as a component that supplementally improves the adhesive strength of the above-mentioned adhesive resin, and is distinguished from the above-mentioned adhesive resin. It will be.

The mass average molecular weight (Mw) of the tackifier is preferably 400 to 9000, more preferably 500 to 8000, still more preferably 800 to 5000.

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

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

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

A tackifier may be used independently, and may use together 2 or more types from which a softening point, a structure, etc. differ.

And when using 2 or more types of some tackifier, it is preferable that the weighted average of the softening points of those some tackifier belongs to the said range.

The content of the tackifier is preferably 0.01 to 65% by mass, relative to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x) or the total amount (100% by mass) of the pressure-sensitive adhesive layer (X). It is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, still more preferably 2 to 30% by mass.

(Additive for adhesive)

1 aspect of this invention WHEREIN: The adhesive composition (x) may contain the additive for adhesive used for general adhesive other than the above-mentioned additive within the range which does not impair the effect of this invention.

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

In addition, these additives for adhesives may be used independently, respectively, and may use 2 or more types together.

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

In addition, when using the support layer (II) of the above-mentioned 2nd aspect which has the 1st adhesive layer (X1) which is an expandable adhesive layer, as a formation material of the 1st adhesive layer (X1) which is an expandable adhesive layer, the above-mentioned In one PSA composition (x), it is formed from an expandable PSA composition (x11) containing thermally expandable particles.

The thermally expandable particles are as described above.

The content of the thermally expandable particles is preferably 1 to 70% by mass, relative to the total amount (100% by mass) of the active ingredients of the expandable PSA composition (x11) or the total amount (100% by mass) of the expandable PSA layer. It is preferably 2 to 60% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 40% by mass.

On the other hand, when the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer, it is preferable that the pressure-sensitive adhesive composition (x) as a forming material of the non-expandable pressure-sensitive adhesive layer does not contain thermally expandable particles.

In the case of containing thermally expandable particles, the content thereof is preferably as small as possible, relative to the total amount (100% by mass) of the active ingredient of the PSA composition (x) or the total amount (100% by mass) of the PSA layer (X), It is preferably less than 1 mass%, more preferably less than 0.1 mass%, even more preferably less than 0.01 mass%, still more preferably less than 0.001 mass%.

In addition, when using the support layer (II) which has a 1st adhesive layer (X1) and a 2nd adhesive layer (X2) which is a non-expandable adhesive layer like the laminated body 2a, 2b shown in FIG. 2, 23 degreeC The storage shear modulus (G'(23)) of the first pressure-sensitive adhesive layer (X1), which is the non-expandable pressure-sensitive adhesive layer in , is preferably 1.0 × 10 ⁸ Pa or less, more preferably 5.0 × 10 ⁷ Pa or less, More preferably, it is 1.0 × 10 ⁷ Pa or less.

When the storage shear modulus (G'(23)) of the first pressure-sensitive adhesive layer (X1) that is the non-expandable pressure-sensitive adhesive layer is 1.0 × 10 ⁸ Pa or less, for example, the same structure as the laminates 2a and 2b shown in FIG. 2 In this case, irregularities are easily formed on the surface of the first pressure-sensitive adhesive layer (X1) in contact with the cured resin layer (I') due to the expansion of the thermally expandable particles in the expandable substrate layer (Y1) by the thermal expansion treatment. lose

As a result, it can be set as a laminated body that can be easily separated from the interface (P) of the support layer (II) and the cured resin layer (I') collectively with a slight force.

The storage shear modulus (G'(23)) of the first pressure-sensitive adhesive layer (X1), which is the non-expandable pressure-sensitive adhesive layer at 23°C, is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 × 10 It is ⁴ Pa or more, More preferably, it is 1.0x10 ^<5> Pa or more.

The light transmittance at a wavelength of 375 nm of the support layer (II) of the laminate of one aspect of the present invention is preferably 30% or more, more preferably 50% or more, still more preferably 70% or more. When the light transmittance is within the above range, when the energy ray curable resin layer (I) is irradiated with energy rays (ultraviolet rays) through the support layer (II), the curing degree of the energy ray curable resin layer (I) is further improved. Although the upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, it is possible, for example, to be 95% or less. The transmittance can be measured according to a known method using a spectrophotometer.

From the viewpoint of achieving the above light transmittance, when the base material (Y) and the pressure-sensitive adhesive layer (X) of the support layer (II) contain a colorant, it is preferable to adjust the content to an extent that does not impair the effect of the present invention. desirable.

In the case of containing a colorant, the content thereof is preferably as small as possible, and relative to the total amount (100% by mass) of the active ingredient of the PSA composition (x) or the total amount (100% by mass) of the PSA layer (X), preferably is less than 1% by mass, more preferably less than 0.1% by mass, even more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass, and the content of the colorant in the base material (Y) is the resin composition (y ), relative to the total amount (100 mass%) of the active ingredient or the total amount (100 mass%) of the substrate (Y), preferably less than 1 mass%, more preferably less than 0.1 mass%, still more preferably 0.01 It is less than mass %, even more preferably less than 0.001 mass %.

<Energy ray curable resin layer (I)>

The energy ray-curable resin layer (I) is not particularly limited as long as it is a layer that can be cured by irradiation with energy ray, and is formed, for example, from an energy ray-curable resin composition containing an energy ray-curable component (a).

[Energy ray curable component (a)]

The energy ray-curable component (a) is a component that is cured by energy ray irradiation.

As the energy ray-curable component (a), a polymer (a1) having an energy ray-curable double bond and having a mass average molecular weight (Mw) of 80000 to 2000000 (hereinafter, simply referred to as "polymer (a1)"), an energy ray-curable double Compound (a2) having a bond and having a molecular weight of 100 to 80000 (hereinafter, simply referred to as "compound (a2)"); and the like.

The energy ray-curable component (a) may be used alone or in combination of two or more.

(Polymer (a1))

The polymer (a1) is a polymer having an energy ray-curable double bond and having a mass average molecular weight (Mw) of 80000 to 2000000.

As the polymer (a1), for example, an acrylic polymer (a11) having a functional group X capable of reacting with a group of another compound, and an energy ray-curable compound (a12) having a group Y and an energy ray-curable double bond capable of reacting with the functional group X (a12). ) and acrylic resin (a1-1) formed by polymerization.

A polymer (a1) may be used independently and may use 2 or more types together.

・Acrylic polymer (a11)

The functional group X of the acrylic polymer (a11) is, for example, selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, a substituted amino group (a group in which one or two hydrogen atoms of an amino group are substituted with groups other than hydrogen atoms), and an epoxy group. One or more types can be mentioned.

Examples of the acrylic polymer (a11) include those formed by copolymerization of an acrylic monomer having the functional group X and an acrylic monomer not having the functional group X, and in addition to these monomers, further monomers other than the acrylic monomer (not acrylic monomer) may be copolymerized. The acrylic polymer (a11) may be a random copolymer or a block copolymer.

The acrylic polymer (a11) may be used alone or in combination of two or more.

Examples of the acrylic monomer having the functional group X include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, a substituted amino group-containing monomer, and an epoxy group-containing monomer.

Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate. ) Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and non-(meth)acrylic unsaturated alcohols (unsaturated alcohols having no (meth)acryloyl backbone) such as vinyl alcohol and allyl alcohol.

Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds) such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; anhydrides of the above ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkyl esters such as 2-carboxyethyl methacrylate; and the like.

Among these, a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.

Examples of the acrylic monomer having no functional group X include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (Lauryl (meth)acrylate), Tridecyl (meth)acrylate, Tetradecyl (meth)acrylate (Myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Hexadecyl (meth)acrylate (Palmyl (meth)acrylate) ethyl), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc., wherein the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms (meth)acrylate alkyl Ester etc. are mentioned.

Moreover, as an acryl-type monomer which does not have the said functional group X, For example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc. (meth)acrylic acid ester containing an alkoxyalkyl group; (meth)acrylic acid esters having an aromatic group including (meth)acrylic acid aryl esters such as phenyl (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid esters having non-crosslinkable tertiary amino groups, such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; and the like.

Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; Styrene etc. are mentioned.

In the acrylic polymer (a11), the content of the amount of structural units derived from the acrylic monomer having the functional group X relative to the total amount of the structural units constituting this is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, more preferably 3 to 30% by mass. When the content of the structural unit is in the above range, the content of the energy ray-curable double bond in the obtained acrylic resin (a1-1) can be easily adjusted to a preferable range.

・Energy ray curable compound (a12)

The energy ray-curable compound (a12) is a compound having a group Y that reacts with the functional group X and an energy ray-curable double bond.

As said group Y, 1 or more types chosen from the group which consists of an isocyanate group, an epoxy group, and a carboxy group are mentioned, for example, and among these, an isocyanate group is preferable. When the energy ray-curable compound (a12) has an isocyanate group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The number of energy ray-curable double bonds in the energy ray-curable compound (a12) is preferably 1 to 5, more preferably 1 to 3, in one molecule.

The energy ray-curable compound (a12) may be used alone or in combination of two or more.

Examples of the energy ray-curable compound (a12) include 2-methacryloyloxyethyl isocyanate, meta-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloyloxymethyl) ethyl isocyanate; Acryloyl monoisocyanate compound obtained by reaction of a diisocyanate compound or a polyisocyanate compound, and hydroxyethyl (meth)acrylate; The acryloyl monoisocyanate compound etc. which are obtained by reaction of a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth)acrylate are mentioned. Among these, 2-methacryloyloxyethyl isocyanate is preferable.

In the acrylic resin (a1-1), the ratio of the content of the energy ray-curable double bond derived from the energy ray-curable compound (a12) to the content of the functional group X derived from the acrylic polymer (a11) is preferably 20 to 120 mol%, more preferably 5 to 100 mol%, still more preferably 50 to 100 mol%. When the ratio is within the above range, the adhesive force of the cured resin layer (I') formed by curing becomes larger. In addition, when the energy ray-curable compound (a12) is a monofunctional (having one of the above groups in one molecule) compound, the upper limit of the ratio of the above content is 100 mol%, but the energy ray-curable compound (a12) is polyfunctional In the case of a compound (having two or more of the above groups in one molecule), the upper limit of the ratio of the above content may exceed 100 mol%.

The content of the acrylic resin (a1-1) is preferably based on the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). It is 1-40 mass %, More preferably, it is 2-30 mass %, More preferably, it is 3-20 mass %.

The mass average molecular weight (Mw) of the polymer (a1) is preferably 100000 to 2000000, more preferably 300000 to 1500000.

At least a part of the polymer (a1) may be crosslinked with a crosslinking agent (e) described below, or may not be crosslinked.

(Compound (a2))

The compound (a2) is a compound having an energy ray-curable double bond and having a molecular weight of 100 to 80000.

As an energy ray-curable double bond which the compound (a2) has, a (meth)acryloyl group, a vinyl group, etc. are preferable.

Examples of the compound (a2) include a low-molecular-weight compound having an energy ray-curable double bond, an epoxy resin having an energy ray-curable double bond, and a phenol resin having an energy ray-curable double bond.

A compound (a2) may be used independently or may use 2 or more types together.

Examples of the low-molecular-weight compound having an energy ray-curable double bond include polyfunctional monomers and oligomers, and an acrylate-based compound having a (meth)acryloyl group is preferable.

Examples of the acrylate-based compound include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth) )Acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryl Roxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypro Poxy)phenyl]propane, tricyclodecanedimethyloldi(meth)acrylate (tricyclodecanedimethyloldi(meth)acrylate), 1,10-decanedioldi(meth)acrylate, 1,6-hexanedioldi (meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly Tetramethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth) ) acryloxyethoxy) phenyl] propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, etc. bifunctional (meth)acrylate; Tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified tris-(2-(meth)acryloxyethyl)isocyanurate, ethoxylated glycerin tri(meth)acrylate, pentaerythate Lithol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate polyfunctional (meth)acrylates such as dipentaerythritol poly(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Polyfunctional (meth)acrylate oligomers, such as a urethane (meth)acrylate oligomer, etc. are mentioned.

As the epoxy resin having an energy ray-curable double bond and the phenol resin having an energy ray-curable double bond, those described in, for example, Paragraph 0043 of "Japanese Patent Laid-Open No. 2013-194102" can be used. Such a resin also corresponds to a resin constituting the thermosetting component (f) described later, but is handled as a compound (a2) in the present invention.

The mass average molecular weight (Mw) of the compound (a2) is preferably from 100 to 30000, more preferably from 300 to 10000.

The content of the compound (a2) is preferably 1 to 40 relative to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). It is mass %, More preferably, it is 2-30 mass %, More preferably, it is 3-20 mass %.

[Polymer (b) not having an energy ray-curable double bond]

When the energy ray-curable resin composition contains the compound (a2), it is preferable to further contain a polymer (b) having no energy ray-curable double bond (hereinafter, simply referred to as "polymer (b)").

A polymer (b) may be used independently and may use 2 or more types together.

Examples of the polymer (b) include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, and polyester urethane resins. . Among these, an acrylic polymer (hereinafter also referred to as "acrylic polymer (b-1)") is preferable.

The acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one type of acrylic monomer, or a copolymer of two or more types of acrylic monomers, and one or two or more types of acrylic monomers and , 1 type or 2 or more types of copolymers with monomers other than acrylic monomers (non-acrylic monomers) may be sufficient.

Examples of the acrylic monomer constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having a cyclic backbone, glycidyl group-containing (meth)acrylic acid esters, and hydroxyl group-containing ( meth)acrylic acid esters, substituted amino group-containing (meth)acrylic acid esters, and the like. Here, the "substituted amino group" is as described above.

Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. ) isobutyl acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate ) Isooctyl acrylate, (meth) acrylate n-octyl, (meth) acrylate n-nonyl, (meth) isononyl acrylate, (meth) decyl acrylate, (meth) undecyl acrylate, dodecyl (meth) acrylate (( lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate (palmityl (meth)acrylate) , (meth)acrylate alkyl esters in which the alkyl group constituting the alkyl ester has a chain structure of 1 to 18 carbon atoms, such as heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. can be heard

Examples of (meth)acrylic acid esters having a cyclic skeleton include (meth)acrylic acid cycloalkyl esters such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; (meth)acrylic acid aralkyl esters such as benzyl (meth)acrylate; (meth)acrylic acid cycloalkenyl esters such as (meth)acrylic acid dicyclopentenyl ester; (meth)acrylic acid cycloalkenyloxyalkyl esters such as (meth)acrylic acid dicyclopentenyloxyethyl ester; and the like.

As a glycidyl group-containing (meth)acrylic acid ester, glycidyl (meth)acrylate etc. are mentioned, for example.

Examples of the hydroxyl group-containing (meth)acrylic acid ester include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Propyl, (meth)acrylate 2-hydroxybutyl, (meth)acrylate 3-hydroxybutyl, (meth)acrylate 4-hydroxybutyl, etc. are mentioned.

Examples of the substituted amino group-containing (meth)acrylic acid ester include N-methylaminoethyl (meth)acrylic acid.

Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; Styrene etc. are mentioned.

The polymer (b) may or may not be crosslinked at least in part with the crosslinking agent (e).

As a polymer (b) at least one part crosslinked by the crosslinking agent (e), what the reactive functional group in a polymer (b) reacted with the crosslinking agent (e) is mentioned, for example.

What is necessary is just to select the said reactive functional group suitably according to the kind of crosslinking agent (e) etc., and it is not specifically limited. For example, when the crosslinking agent (e) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, and an amino group, and among these, a hydroxyl group highly reactive with an isocyanate group is preferable. . In the case where the crosslinking agent (e) is an epoxy compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like, and among these, a carboxyl group highly reactive with an epoxy group is preferable. However, in terms of preventing corrosion of circuits of semiconductor wafers and semiconductor chips, the reactive functional group is preferably a group other than a carboxy group.

As a polymer (b) which has the said reactive functional group, what was obtained by polymerizing the monomer which has at least the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), one or both of the acrylic monomer and the non-acrylic monomer mentioned as monomers constituting this may be used as those having the reactive functional group. For example, as a polymer (b) which has a hydroxyl group as a reactive functional group, what was obtained by polymerizing (meth)acrylic acid ester containing a hydroxyl group is mentioned, for example, In addition to that, in the said acrylic monomer or non-acrylic monomer mentioned above , those obtained by polymerizing a monomer formed by substituting one or two or more hydrogen atoms with the above-mentioned reactive functional groups.

In the polymer (b), the content of structural units derived from monomers having reactive functional groups relative to the total amount of structural units constituting this is preferably 1 to 25% by mass, more preferably 2 to 20% by mass. . When the content of the structural unit is within the above range, the degree of crosslinking in the polymer (b) falls within a more preferable range.

The mass average molecular weight (Mw) of the polymer (b) is preferably from 10000 to 2000000, more preferably from 100000 to 1500000, from the viewpoint of improving the film-forming properties of the energy ray-curable resin composition.

Examples of the energy ray-curable resin composition include those containing either or both of the polymer (a1) and the compound (a2), and when the compound (a2) is contained, it is preferable to further contain the polymer (b) as well. do.

The total content of the energy ray-curable component (a) and the polymer (b) is the total amount of the active ingredients of the energy ray-curable resin composition (100% by mass) or the total amount of the energy ray-curable resin layer (I) (100% by mass) , it is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 15 to 70% by mass. When the total content is within the above range, the energy ray curability becomes better.

When the energy ray curable resin composition or the energy ray curable resin layer (I) contains the energy ray curable component (a) and the polymer (b), the content of the polymer (b) is 100 parts by mass of the energy ray curable component (a) , preferably from 3 to 160 parts by mass, more preferably from 6 to 130 parts by mass. When the content of the polymer (b) is within the above range, energy ray curability becomes better.

The energy ray curable resin composition, in addition to the energy ray curable component (a) and the polymer (b), depending on the purpose, a photopolymerization initiator (c), a coupling agent (d), a crosslinking agent (e), a colorant (g), a heat curable You may contain at least 1 type chosen from the group which consists of a component (f), a hardening accelerator (g), a filler (h), and a general-purpose additive (z). For example, the energy-beam-curable resin layer (I) formed by using an energy-beam-curable resin composition containing an energy-beam curable component (a) and a heat-curable component (f) has adhesive strength to an adherend by heating. This improves, and the strength of the cured resin layer (I') formed from this energy ray-curable resin layer (I) is also improved.

[Photoinitiator (c)]

Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds, such as; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2,2-dimethoxy-1,2-diphenylethane-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; Benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H benzophenone compounds such as -carbazol-3-yl]-,1-(O-acetyloxime); peroxide compounds; diketone compounds such as diacetyl; benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; 2-chloro anthraquinone etc. are mentioned. Moreover, quinone compounds, such as 1-chloro anthraquinone; Photosensitizers, such as an amine, etc. can also be used.

A photoinitiator (c) may be used independently and may use 2 or more types together.

The content of the photopolymerization initiator (c) in the energy ray curable resin composition or the energy ray curable resin layer (I) is preferably from 0.01 to 20 parts by mass, more preferably from 0.01 to 20 parts by mass, based on 100 parts by mass of the energy ray curable compound (a). is 0.03 to 10 parts by mass, more preferably 0.05 to 5 parts by mass.

[Coupling agent (d)]

As the coupling agent (d), by using an inorganic compound or organic compound and one having a reactive functional group, the adhesion of the energy ray curable resin layer (I) can be improved, and the energy ray curable resin layer (I) can be cured. The cured resin layer (I') formed by the above has improved water resistance without impairing heat resistance.

A coupling agent (d) may be used independently and may use 2 or more types together.

The coupling agent (d) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray-curable component (a), polymer (b), or the like, and more preferably a silane coupling agent.

Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxysilane. Diloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2 -Aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3- ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, methyltrie Toxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. are mentioned.

The content of the coupling agent (d) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is preferably from 0.03 to 20 with respect to 100 parts by mass in total of the energy ray-curable component (a) and the polymer (b). Part by mass, more preferably 0.05 to 10 parts by mass, still more preferably 0.1 to 5 parts by mass. When the content of the coupling agent (d) is equal to or greater than the lower limit, effects such as improvement in the dispersibility of the filler to resin and improvement in the adhesiveness of the energy ray-curable resin layer (I) are obtained more remarkably, and when the content is equal to or less than the upper limit, Generation of outgas is suppressed.

[Crosslinking agent (e)]

By crosslinking the energy ray-curable component (a), the polymer (b) and the like using the crosslinking agent (e), the initial adhesive force and cohesive force of the energy ray-curable resin layer (I) can be adjusted.

A crosslinking agent (e) may be used independently and may use 2 or more types together.

Examples of the crosslinking agent (e) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents (crosslinking agents having an aziridinyl group), and the like.

As an organic polyhydric isocyanate compound, For example, an aromatic polyhydric isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyhydric isocyanate compound (Hereinafter, these compounds are collectively called "aromatic polyhydric isocyanate compound etc."); Trimers, isocyanurate bodies, and adduct bodies, such as the said aromatic polyhydric isocyanate compound; Terminal isocyanate urethane prepolymer obtained by making the said aromatic polyhydric isocyanate compound etc. and a polyol compound react, etc. are mentioned.

The "adduct body" is an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound or an alicyclic polyvalent isocyanate compound, and a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil means a reactant of, and examples thereof include xylylene diisocyanate adducts of trimethylolpropane as described below. In addition, "terminal isocyanate urethane prepolymer" means a prepolymer having an isocyanate group at the terminal portion of the molecule while having a urethane bond.

More specifically as an organic polyhydric isocyanate compound, For example, 2, 4- tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Compounds in which any one or two or more of tolylene diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are added to all or some hydroxyl groups of polyols such as trimethylolpropane; Lysine diisocyanate etc. are mentioned.

Examples of the organic polyvalent imine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide)triethylenemelamine, and the like.

When using an organic polyhydric isocyanate compound as the crosslinking agent (e), it is preferable to use a hydroxyl group-containing polymer as the energy ray-curable component (a) and/or polymer (b). When the crosslinking agent (e) has an isocyanate group and the energy ray curable component (a) and/or the polymer (b) have a hydroxyl group, the reaction between the crosslinking agent (e) and the energy ray curable component (a) and/or the polymer (b) By this, a crosslinked structure can be easily introduced into the energy ray-curable resin layer (I).

The content of the crosslinking agent (e) in the energy ray curable resin composition or the energy ray curable resin layer (I) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass in total of the energy ray curable component (a) and the polymer (b). part, more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass.

[Heat curable component (f)]

Examples of the thermosetting component (f) include epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins. Among these, epoxy thermosetting resins are preferable. .

The thermosetting component (f) may be used alone or in combination of two or more.

(epoxy-based thermosetting resin)

The epoxy-based thermosetting resin contains the epoxy resin (f1) and may further contain a thermosetting agent (f2).

Examples of the epoxy resin (f1) include known epoxy resins, such as polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolak epoxy resins, and dicyclopentadiene type epoxy resins. and bifunctional or higher functional epoxy compounds such as biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins.

Epoxy resin (f1) may be used independently or may use 2 or more types together.

As the epoxy resin (f1), an epoxy resin having an unsaturated hydrocarbon group such as ethenyl group (vinyl group), 2-propenyl group (allyl group), (meth)acryloyl group, and (meth)acrylamide group may be used. An epoxy resin having an unsaturated hydrocarbon group has higher compatibility with acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. Therefore, reliability of the obtained package is improved by using an epoxy resin having an unsaturated hydrocarbon group.

The number average molecular weight of the epoxy resin (f1) is preferably 300 to 30000, more preferably 400, from the viewpoint of the curability of the energy ray curable resin layer (I) and the strength and heat resistance of the cured resin layer (I'). to 10000, more preferably 500 to 3000.

The epoxy equivalent of the epoxy resin (f1) is preferably 100 to 1000 g/eq, more preferably 150 to 800 g/eq.

The thermal curing agent (f2) functions as a curing agent for the epoxy resin (f1).

Examples of the thermal curing agent (f2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxy group, and a group in which an acid group is anhydride, and a phenolic hydroxyl group, an amino group, or a group in which an acid group is anhydride is preferable, and phenol It is more preferable that it is a sexual hydroxyl group or an amino group.

A heat curing agent (f2) may be used independently or may use 2 or more types together.

Among the thermal curing agents (f2), examples of the phenolic curing agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. can be heard

Among the thermal curing agents (f2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.

The content of the thermal curing agent (f2) is preferably from 0.01 to 20 parts by mass relative to 100 parts by mass of the epoxy resin (f1).

The content of the heat curable component (f) (for example, the total content of the epoxy resin (f1) and the heat curing agent (f2)) is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the polymer (b).

[Curing accelerator (g)]

The curing accelerator (g) is a component for adjusting the curing speed of the energy ray-curable resin layer (I).

Examples of the preferable curing accelerator (g) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; Tetraphenyl boron salts, such as tetraphenylphosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate, etc. are mentioned.

When using a hardening accelerator (g), content of a hardening accelerator (g) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermosetting component (f).

[Universal additive (z)]

The general-purpose additive (z) may be a known one, can be arbitrarily selected according to the purpose, and is not particularly limited. Examples thereof include a filler, a colorant, a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. .

The general-purpose additives (z) may be used alone or in combination of two or more.

As a filler, an inorganic filler, an organic filler, etc. are mentioned, By using these, the thermal expansion coefficient of cured resin layer (I') can be adjusted.

The energy ray-curable resin layer (I) may or may not contain a filler, but when it contains a filler, its content is, from the viewpoint of more effectively suppressing the occurrence of warping, the energy ray-curable resin composition It is preferably 5 to 87 mass%, more preferably 7 to 78 mass% with respect to the total amount (100 mass%) of the active ingredient or the total amount (100 mass%) of the energy ray-curable resin layer (I).

As a filler, what consists of a heat conductive material is mentioned, for example.

Examples of the inorganic filler include powders such as silica, alumina, talc, calcium carbonate, titanium white, bengala, silicon carbide, and boron nitride; Beads which spheroidized these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; Glass fiber etc. are mentioned.

The average particle diameter of the filler is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, still more preferably 0.3 to 10 μm. When the average particle diameter of the filler is within the above range, the decrease in transmittance of the energy ray curable resin layer (I) can be suppressed while maintaining the adhesiveness of the cured resin layer (I').

The energy ray curable resin composition may or may not contain a colorant, but when it contains a colorant, the smaller the content, the more preferable it is. Specifically, the active ingredient of the energy ray curable resin composition It is preferably less than 5% by mass, more preferably less than 0.1% by mass, still more preferably 0.01% by mass relative to the total amount (100% by mass) or the total amount (100% by mass) of the energy ray-curable resin layer (I). %, even more preferably less than 0.001% by mass.

<<Method for Producing Energy Ray Curable Resin Composition>>

The energy ray-curable resin composition is obtained by blending each component for constituting it.

The order of adding each component at the time of blending is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be used by mixing the solvent with any combination component other than the solvent and diluting the combination component in advance, or mixing the solvent with these combination components without diluting any combination component other than the solvent in advance. You may use by mixing.

The method of mixing each component at the time of compounding is not specifically limited, The method of mixing by rotating a stirrer or a stirring blade etc.; How to mix using a mixer; What is necessary is just to select suitably from well-known methods, such as the method of mixing by applying ultrasonic waves.

The temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component does not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30°C.

Examples of the solvent include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; esters such as ethyl acetate; Ketones, such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone; and the like. Among these, methyl ethyl ketone, toluene, and ethyl acetate are preferable from the viewpoint of being able to more uniformly mix the components contained in the energy ray-curable resin composition. A solvent may be used independently and may use 2 or more types together.

The energy ray-curable resin layer (I) may have a single-layer structure or a plurality of layers of two or more layers.

As the energy ray-curable resin layer (I) composed of two or more layers, for example, an energy ray-curable resin layer (I-i) for imparting a cured resin layer (I') having a high storage modulus (E'); , those having an energy ray-curable resin layer (I-ii) having high adhesive strength. In the case of having such a structure, by arranging the energy ray-curable resin layer (I-ii) on the surface on the side where the object to be sealed is mounted, the object to be sealed can be firmly fixed, and after curing, the energy ray-curable water Since the cured resin layer (I') formed by curing the ground layer (I-i) effectively suppresses warpage, the performance as a temporarily fixed layer and the performance as a warpage prevention layer can be more highly compatible. The preferred composition and physical properties of the energy ray-curable resin layers (I-i) and (I-ii) may be appropriately selected and applied according to the desired function from among the preferred compositions and physical properties of the energy ray-curable resin layer (I) described above.

The thickness of the energy ray-curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, still more preferably 10 to 200 μm, even more preferably 15 to 100 μm, still more preferably is 20 to 50 μm. When the thickness of the energy ray-curable resin layer (I) is equal to or greater than the lower limit above, a cured encapsulated body with curvature suppressed more effectively can be obtained. is obtained

Here, the "thickness of the energy ray-curable resin layer (I)" means the thickness of the entire energy ray-curable resin layer (I), for example, the thickness of the energy ray-curable resin layer (I) composed of two or more layers. means the total thickness of all layers constituting the energy ray-curable resin layer (I).

The storage modulus (E') of the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) at 23°C is a cured encapsulated body with a cured resin layer that suppresses warpage and has a flat surface. From the viewpoint of a laminate that can be produced, it is preferably 1.0 × 10 ⁷ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more, still more preferably 5.0 × 10 ⁸ Pa or more, still more preferably 1.0 × 10 ⁹ or more. , Again, preferably 1.0 × 10 ¹³ Pa or less, more preferably 1.0 × 10 ¹² Pa or less, still more preferably 5.0 × 10 ¹¹ Pa or less, still more preferably 1.0 × 10 ¹¹ Pa or less.

The visible light (wavelength: 380 nm to 750 nm) transmittance of the energy ray-curable resin layer (I) is preferably 5% or more, more preferably 10% or more, even more preferably 30% or more, still more preferably 50% or more. more than 1% When the visible light transmittance is within the above range, sufficient energy ray curability is obtained. The upper limit of the visible light transmittance is not particularly limited, but may be, for example, 95% or less. The transmittance can be measured according to a known method using a spectrophotometer.

<Manufacturing method of laminated body>

In the laminate of one embodiment of the present invention, for example, the pressure-sensitive adhesive layer (X), the base material (Y), and the energy ray-curable resin layer (I) are separately formed, and these are bonded together so as to have a desired configuration. ) can be produced by Formation of each layer can be formed by apply|coating and drying the resin composition for forming each layer on a peeling material, for example.

However, the manufacturing method of the laminated body of one aspect of this invention is not limited to the said method, For example, resin for forming the base material (Y) on the adhesive layer (X) formed on the release material Like a method of applying the composition (y) and then further applying an energy ray-curable resin composition thereon, a method of applying a resin composition sequentially on a specific layer and forming a layer to form a multilayer may be used. In that case, you may apply|coat several layers simultaneously using a multilayer coater etc., for example.

[Method for producing cured encapsulation]

The method for producing a cured encapsulated body of one aspect of the present invention is a method for producing a cured encapsulated body using the laminate of one aspect of the present invention, and includes the following steps (i) to (iv).

Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate

Step (ii): Step of forming a cured resin layer (I′) obtained by curing the energy ray-curable resin layer (I) by irradiating the energy ray-curable resin layer (I) with an energy ray

Step (iii): Covering the surfaces of the object to be sealed and the cured resin layer (I′) at least around the object to be sealed with a thermosetting encapsulant, and curing the encapsulant by heat, including the object to be encapsulated Process of forming cured encapsulation

Step (iv): Step of separating the cured resin layer (I′) and the support layer (II) at the interface by the treatment of expanding the thermally expandable particles to obtain a cured encapsulated body with a cured resin layer

The cured encapsulant in one aspect of the present invention is formed by coating an object to be encapsulated with a encapsulant and curing the encapsulant, and is constituted by a cured product of the object to be encapsulated and the encapsulant.

Fig. 4 is a cross-sectional schematic view showing a step of manufacturing a curing encapsulated body using the layered product 1a shown in Fig. 1(a). Hereinafter, each process mentioned above is demonstrated, referring FIG. 4 suitably.

<Process (i)>

Step (i) is a step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate of one aspect of the present invention.

4(a), in this step, the adhesive surface of the adhesive layer (X) of the support layer (II) is affixed to the support body 50 using the layered product 1a, and the energy ray-curable resin layer (I) A state in which the object to be sealed 60 is placed on a part of the surface is shown.

In Fig. 4(a), an example using the laminate 1a shown in Fig. 1(a) is shown, but in the case of using a laminate of one aspect of the present invention having a different configuration, the same , the support, the layered product, and the object to be sealed are laminated or placed in this order.

As the temperature conditions in the step (i), it is preferable to carry out at a temperature at which the thermally expandable particles do not expand, for example, in an environment of 0 to 80 ° C. (provided that the expansion start temperature (t) is 60 to In the case of 80°C, it is preferably carried out in an environment lower than the expansion start temperature (t).

It is preferable that a support body is affixed on the whole surface of the adhesive surface of adhesive layer (X) of a laminated body.

Therefore, the support is preferably plate-shaped. Moreover, as shown in FIG. 4, it is preferable that the area of the adhesive surface of adhesive layer (X) and the surface of the support body on the side to be stuck is more than the area of the adhesive surface of adhesive layer (X).

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

As a material which comprises a specific support body, For example, metal materials, such as SUS; non-metallic inorganic materials such as glass and silicon wafer; resin materials such as epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, polyimide resins, and polyamideimide resins; Composite materials, such as a glass epoxy resin, etc. are mentioned, Among these, SUS, glass, a silicon wafer, etc. are preferable. Moreover, from the viewpoint of making it possible to irradiate the energy ray-curable resin layer (I) with energy rays through the support, it is preferable that the support is a transparent material such as glass.

In addition, examples of engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).

Examples of super engineering plastics include polyphenylene sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).

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

On the other hand, as objects to be sealed placed on a part of the surface of the energy ray-curable resin layer (I), for example, semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, substrates for panels, etc. can be heard

When the object to be sealed is a semiconductor chip, a semiconductor chip with a cured resin layer can be manufactured by using the laminate of one aspect of the present invention.

Conventionally known semiconductor chips can be used, and integrated circuits composed of circuit elements such as transistors, resistors, and capacitors are formed on the circuit surface.

And it is preferable that the semiconductor chip is mounted so that the back surface on the opposite side to the circuit surface may be covered with the surface of the energy ray-curable resin layer (I). In this case, after mounting, the circuit surface of the semiconductor chip is exposed.

A well-known device such as a flip chip bonder or a die bonder can be used for mounting the semiconductor chip.

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

Here, in the laminate of one embodiment of the present invention, as in FOWLP, FOPLP, etc., a semiconductor chip is covered with an encapsulant over a region larger than the chip size to form a redistribution layer not only on the circuit surface of the semiconductor chip but also on the surface area of the encapsulant It is preferable to apply to a package that does.

Therefore, the semiconductor chips are placed on a part of the surface of the energy ray-curable resin layer (I), and it is preferable that a plurality of semiconductor chips are placed on the surface in a state aligned at regular intervals. It is more preferable that the semiconductor chips are placed on the surface in a state aligned in a matrix of a plurality of rows and a plurality of columns at regular intervals.

The distance between the semiconductor chips may be appropriately determined depending on the shape of the target package or the like.

<Process (ii)>

Step (ii) is a step of irradiating the energy ray-curable resin layer (I) with energy rays to form a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I).

Fig. 4(b) shows a state in which the cured resin layer (I') is formed by curing the energy ray-curable resin layer (I) in this step.

The type and irradiation conditions of the energy ray are not particularly limited as long as they are cured to the extent that the energy ray-curable resin layer (I) sufficiently exhibits its function, and may be appropriately selected from known methods according to the desired process.

It is preferable that the energy beam illuminance at the time of curing of the energy beam curable resin layer (I) is 4 to 280 mW/cm 2 , and the light quantity of the energy beam at the time of curing is 5 to 1000 mJ/cm 2 . It is preferable, and 100-500 mJ/cm<2> is more preferable.

The type of energy ray and the irradiation device are as described above.

The energy ray may be irradiated from any direction as long as the energy ray-curable resin layer (I) can be irradiated with the energy ray. For example, as the support body (II) and the support body 50, those having excellent light transmittance By using, through the support body (II) and the support body 50 (that is, incident from the surface on the opposite side of the pressure-sensitive adhesive layer (X) of the support body 50 in Fig. 4 (b), The energy ray can be irradiated to the energy ray-curable resin layer (I) through the pressure-sensitive adhesive layer (X) and the base material (Y)).

<Process (iii)>

Step (iii) covers the surface of the object to be sealed and the cured resin layer (I′) at least in the periphery of the object to be sealed with a thermosetting sealing material (hereinafter also referred to as “coating treatment”), the sealing material It is a step of thermally curing to form a cured encapsulation body containing the object to be encapsulated.

In the covering treatment, first, the object to be sealed and at least the periphery of the object to be sealed on the surface of the cured resin layer (I') are coated with a sealing material.

The sealing material is also filled in gaps between a plurality of semiconductor chips while covering the entire exposed surface of the object to be sealed.

For example, Fig. 4(c) shows a state covered with the sealing material 70 so as to cover both the surfaces of the object to be sealed 60 and the cured resin layer (I').

The sealing material has a function of protecting the object to be sealed and the elements incident thereto from the external environment.

The sealing material used in the manufacturing method of one aspect 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, pellet, film, or liquid in the form of a composition, but from the viewpoint of workability, a sealing resin film that is a film-shaped sealing material is preferable.

As the coating method, it can be appropriately selected and applied according to the type of encapsulant from among methods applied to the conventional encapsulation process, and examples thereof include a roll lamination method, a vacuum press method, a vacuum lamination method, a spin coat method, and a die. A coating method, a transfer molding method, a compression molding molding method, and the like can be applied.

Then, after performing the coating treatment, the sealing material is thermally cured to obtain a cured sealing body in which the object to be sealed is sealed with the sealing material.

Further, the thermal curing treatment in step (iii) is performed at a temperature at which the thermally expandable particles do not expand. For example, when a laminate having a layer containing the thermally expandable particles is used, the thermally expandable particles expand. It is preferably carried out under temperature conditions below the starting temperature (t).

In the manufacturing method of one aspect of the present invention, as shown in Fig. 4 (c), in the state where the cured resin layer (I ') is formed on the surface of the object to be sealed 60 sealed with the sealing material 70, A heat curing treatment is performed.

Since the cured resin layer (I') is formed, it is thought that the difference in shrinkage stress between the two surfaces of the obtained cured encapsulated body can be reduced, and warpage occurring in the cured encapsulated body can be effectively suppressed.

<Process (iv)>

Step (iv) is a step of separating the cured resin layer (I′) and the support layer (II) at the interface by the treatment of expanding the thermally expandable particles to obtain a cured encapsulated body with a cured resin layer.

Fig. 4(d) shows a state in which the cured resin layer (I') and the support layer (II) are separated at the interface (P) by the treatment of expanding the thermally expandable particles.

As shown in FIG. 4(d), a hardened rod with a hardened resin layer having a hardened sealing body 80 formed by sealing the object to be sealed 60 and a hardened resin layer (I') by separating at the interface P. A retard (100) can be obtained.

In addition, the existence of the cured resin layer (I') protects the object to be sealed and contributes to the improvement of the reliability of the object to be sealed while having a function capable of effectively suppressing warpage occurring in the cured encapsulation body.

The "expanding treatment" in step (iv) is a treatment of expanding the thermally expandable particles by heating at or above the expansion start temperature (t) of the thermally expandable particles, and by this treatment, the cured resin layer (I' ) side of the support layer (II), irregularities are formed on the surface. As a result, they can be easily separated at the interface P with a slight force.

As the "temperature equal to or higher than the expansion start temperature (t)" at the time of expanding the thermally expandable particles, it is preferable to be "expansion start temperature (t) + 10°C" or higher and "expansion start temperature (t) + 60°C" or lower, and "expansion start temperature (t) + 60°C" or lower. It is more preferable that it is "start temperature (t) + 15 degreeC" or more and "expansion start temperature (t) + 40 degreeC" or less.

In addition, the heating method is not particularly limited, and examples thereof include a heating method using a hot plate, an oven, a firing furnace, an infrared lamp, a hot air blower, and the like. From the viewpoint of facilitating separation at the interface P, a method in which a heat source during heating can be provided on the side of the support 50 is preferable.

The cured encapsulated body with a cured resin layer obtained in this way is further subjected to necessary processing thereafter. An example thereof is described below. In addition, in the following description, the aspect using the semiconductor chip 60 as the object to be sealed 60 is demonstrated.

<1st grinding process>

Fig. 5 (a) shows the cured encapsulated body 100 with a cured resin layer obtained by the above manufacturing method, and in Fig. 5 (b), the side opposite to the cured resin layer (I') of the cured encapsulated body 80 A first grinding step of exposing the circuit surface 60a of the semiconductor chip 60 by grinding the surface 100a of the semiconductor chip 60 with the grinding means 110 is shown.

It does not specifically limit as grinding means 110, What is necessary is just to implement using well-known grinding apparatuses, such as a grinder.

When performing the 1st grinding process, it is preferable to fix the surface of the cured resin layer (I') side of a cured encapsulation body on another support body from a viewpoint of workability|operativity.

Moreover, from the viewpoint of workability, you may dicing to a predetermined size including one or a plurality of chips before the first grinding step.

<Rewiring layer and external terminal electrode formation process>

5(c), the redistribution layer 200 and the external terminal electrode ( 300), a redistribution layer and an external terminal electrode forming process are shown.

The material of the redistribution layer 200 is not limited as long as it is a conductive material, and examples thereof include metals such as gold, silver, copper, and aluminum, alloys containing these metals, and the like. The redistribution layer 200 can be formed by a known method such as a subtractive method or a semi-additive method, and one or more insulating layers may be formed as necessary.

The external terminal electrode 300 is electrically connected to the external electrode pad of the redistribution layer 200 . The external electronic electrode 300 can be formed, for example, by solder-joining solder balls or the like.

<Dicing process>

5(d) shows a step of dicing the cured encapsulated body 100 with a cured resin layer to which the external terminal electrode 300 is connected.

The dicing may be performed in units of one semiconductor chip, or may be diced into a predetermined size including a plurality of semiconductor chips. The method of dicing the cured encapsulation body 100 with a cured resin layer is not particularly limited, and can be performed by cutting means such as a dicing saw.

<2nd grinding process>

FIG. 5(e) shows a second grinding step of grinding the cured resin layer (I′) disposed on the opposite side of the redistribution layer 200 of the cured encapsulation body 80 by means of the grinding means 110. has been At this time, it is preferable to fix the surface of the curing encapsulation body 80 on the side of the redistribution layer 200 with a back grind tape or the like. As the grinding means 110, the means same as the 1st grinding process are mentioned.

In the second grinding step, part of the cured resin layer (I') may be ground, or all of the cured resin layer (I') may be ground.

By grinding the cured resin layer (I'), the obtained semiconductor package can be further miniaturized. Therefore, from the said viewpoint, it is preferable to grind the whole cured resin layer (I').

On the other hand, when the second grinding step is not performed or when only a part of the cured resin layer (I') is ground, the cured resin layer (I') can also play a role of protecting the back surface of the semiconductor chip 60. can

Example

The present embodiment will be specifically described by the following examples, but the present invention is not limited to the following examples.

In addition, in the following description, curable resin layer (I) shall mean both "energy-beam-curable resin layer (I)" and "heat-curable resin layer."

In addition, the physical property value in each case is a value measured by the following method.

<Mass average molecular weight (Mw)>

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

(Measuring conditions)

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

Column temperature: 40 ℃

Developing solvent: tetrahydrofuran

·Flow rate: 1.0 mL/min

<Measurement of the thickness of each layer>

It was measured using a static pressure thickness meter manufactured by Teklok Co., Ltd. (model number: "PG-02J", standard specifications: based on JIS K 6783, Z 1702, Z 1709).

<Methods for measuring expansion start temperature (t) and maximum expansion temperature of thermally expandable particles>

The expansion start temperature (t) of the thermally expansible particles used in each example was measured by the following method.

To an aluminum cup having a diameter of 6.0 mm (internal diameter of 5.65 mm) and a depth of 4.8 mm, 0.5 mg of thermally expansible particles to be measured are added, and an aluminum lid (diameter of 5.6 mm and thickness of 0.1 mm) is placed thereon to prepare a sample. .

Using a dynamic viscoelasticity measuring device, the height of the sample is measured in a state where a force of 0.01 N is applied to the sample from the top of the aluminum cover by a presser. Then, in a state in which a force of 0.01 N was applied by the presser, heating was performed from 20 ° C. to 300 ° C. at a heating rate of 10 ° C./min, the amount of displacement in the vertical direction of the presser was measured, and the displacement start temperature in the forward direction is taken as the expansion initiation temperature (t).

In addition, the maximum expansion temperature was made into the temperature when the amount of displacement measured by the said method reached the maximum.

<Evaluation of warpage>

The curable resin layer (I) of the sheet for forming the curable resin layer (I) produced in each case was affixed to a silicon wafer (size: 12 inches, thickness: 100 µm).

Next, as a thermosetting resin composition, a resin composition obtained by mixing an epoxy resin (manufactured by Struers, product name “Ephofix Resin”) and a curing agent (manufactured by Struers, product name “Epofix Hardener”) is prepared, and the resin composition was applied to the surface of the silicon wafer on the side opposite to the curable resin layer (I) so as to have a thickness of 30 μm. Thus, a pre-curing measurement sample having curable resin layer (I)/silicon wafer/thermosetting resin composition layer in this order was obtained.

Subsequently, when the curable resin layer (I) is the energy ray curable resin layer (I), ultraviolet ray was irradiated using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Co., Ltd.) at an illuminance of 215 mW/cm 2 and an amount of light of 187 mJ/ It irradiated 3 times under the condition of cm2, and cured the energy ray-curable resin layer (I), and formed the cured resin layer (I'). In the case where the curable resin layer (I) was a thermosetting resin layer (I), it was cured by heating at 180°C for 60 minutes to form a cured resin layer (I'). Thereafter, the thermosetting resin composition was cured by heating to form a thermosetting resin layer, and a cured measurement sample having cured resin layer (I′)/silicon wafer/thermosetting resin layer in this order was obtained.

After curing, the measurement sample was placed on a level table, and then visually observed, and the presence or absence of curvature was evaluated based on the following criteria. In addition, since the "silicon wafer/thermosetting resin layer" part in the measurement sample after curing is a configuration corresponding to a cured encapsulant formed by encapsulating a semiconductor chip with a thermosetting resin, the cured resin layer by this evaluation The performance of (I') as a warpage prevention layer can be evaluated.

A: The amount of warpage is 3 mm or less.

B: The amount of warpage is greater than 3 mm and less than 15 mm.

C: The amount of warpage is 15 mm or more.

In addition, the curvature amount at the time of forming a silicon wafer/thermosetting resin layer in the same procedure as the above, without attaching curable resin layer (I), was 15 mm.

<Evaluation of separability>

After attaching a silicon wafer to the surface of the curable resin layer (I) of the laminate obtained in each case, the curable resin layer (I) was cured by energy rays or heat to form a cured resin layer (I'). Next, by expanding the expandable substrate layer (Y1) by heat expansion treatment, the cured resin layer (I') and the support layer (II) were separated, and the separability was evaluated based on the following criteria. In addition, the curing conditions of the curable resin layer (I) and the thermal expansion treatment conditions of the support layer (II) prepared in each case were the same conditions as those described in Examples 1 to 5 and Reference Example 1 described later.

A: Separation is possible, the appearance of the cured resin layer (I') is good, and there is no glue residue.

B: It can be separated, and the appearance of the cured resin layer (I') is good, but there is paste residue in part.

C: Unseparable, or there is glue residue on the entire surface of the cured resin layer (I'), or the appearance of the cured resin layer (I') is poor.

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

An expandable substrate layer (Y1) with a thickness of 200 μm prepared for storage modulus (E′) measurement was made into a size of 5 mm long × 30 mm wide × 200 μm thick, and a release material was removed to obtain a test sample.

Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), under the conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a temperature increase rate of 3 ° C./min, a frequency of 1 Hz, and an amplitude of 20 μm, predetermined The storage modulus (E') of the test sample at a temperature of

<Storage shear modulus (G') of the first pressure sensitive adhesive layer (X1) and the second pressure sensitive adhesive layer (X2)>

The first pressure sensitive adhesive layer (X1) and the second pressure sensitive adhesive layer (X2) were cut into circular shapes having a diameter of 8 mm, the peeling material was removed, and overlapped to obtain a thickness of 3 mm. This was used as a test sample.

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

<Storage modulus (E') of cured resin layer (I')>

A test piece obtained by curing the curable resin layer (I) obtained in each case was used as a test piece, and a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800") was used at a test start temperature of 0°C, a test end temperature of 300°C, and a temperature rise The storage modulus (E') of the formed cured resin layer (I') was measured at 23 °C under conditions of a speed of 3 °C/min, a frequency of 11 Hz, and an amplitude of 20 µm. In addition, in the case where the curable resin layer (I) is the energy ray curable resin layer (I), the test piece was irradiated with ultraviolet light using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Co., Ltd.), illuminance of 215 mW/cm 2 and light intensity of 187 What was cured by irradiation 3 times under conditions of mJ/cm 2 , and when the curable resin layer (I) was a thermosetting resin layer (I), were cured by heating at 180°C for 60 minutes.

Synthesis Example 1

(Synthesis of "acrylic urethane-based resin" used for expandable substrate layer (Y1))

In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate was mixed with respect to 100 parts by mass of polycarbonate diol (carbonate type diol) having a mass average molecular weight of 1,000, and the equivalent ratio of the hydroxyl group of polycarbonate diol and the isocyanate group of isophorone diisocyanate was 1/ 1, and further adding 160 parts by mass of toluene, and stirring under a nitrogen atmosphere, it was made to react at 80 degreeC for 6 hours or more until the isocyanate group concentration reached a theoretical amount.

Then, a solution obtained by diluting 1.44 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by mass of toluene was added, and the mixture was further reacted at 80°C for 6 hours until the isocyanate groups at both ends disappeared. A urethane prepolymer having an average molecular weight of 2.90,000 was obtained.

Subsequently, in a reaction vessel under a nitrogen atmosphere, 100 parts by mass of the urethane prepolymer obtained above, 117 parts by mass of methyl methacrylate (MMA), 5.1 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA), and 1-thio It heated up to 105 degreeC, adding 1.1 mass parts of glycerol, and 50 mass parts of toluene, and stirring. Then, a solution obtained by further diluting 2.2 parts by mass of a radical initiator (manufactured by Nippon Finechem Co., Ltd., product name “ABN-E”) with 210 parts by mass of toluene was added dropwise over 4 hours into the reaction vessel while maintaining the temperature at 105°C.

It was made to react at 105 degreeC after completion|finish of dripping for 6 hours, and the solution of acrylic urethane type-resin with a mass average molecular weight of 10.5 million was obtained.

[Preparation of Sheet for Forming Support Layer (II)]

Preparation Example 1

(supporting layer (II-A))

A sheet for forming a support layer (II-A) was prepared according to the following procedures (1-1) to (1-4).

The detail of the material used for formation of each layer is as follows.

<adhesive resin>

-Acrylic copolymer (i): 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio), which has a structural unit derived from a raw material monomer, and has a Mw of 600,000 acrylic copolymer.

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

＜Additives＞

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

<Thermally expansible particles>

- Thermally expansible particle A: Kureha Co., Ltd. product name "S2640", expansion start temperature (t) = 208 degreeC, average particle diameter ( _D50 ) = 24 micrometers, 90% particle diameter ( _D90 ) = 49 micrometers.

<release material>

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

• Easy release film: product name "SP-PET381031" manufactured by Lintec Co., Ltd., a release agent layer formed from a silicone-based release agent on one side of a PET film, thickness: 38 µm.

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

5.0 parts by mass of the isocyanate-based crosslinking agent (i) was blended with 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, diluted with toluene, and stirred uniformly to obtain a solid content concentration (active ingredient concentration) of 25 mass parts. % of the pressure-sensitive adhesive composition was prepared.

Then, the pressure-sensitive adhesive composition was applied to the surface of the release agent layer of the heavy release film (hereinafter also referred to as "release treatment surface") to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to obtain a thickness of 5 μm. The 1st adhesive layer (X1) which is a non-thermal expansible adhesive layer was formed.

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

Moreover, the adhesive force in 23 degreeC of the 1st adhesive layer (X1) measured based on the said method was 0.3 N/25 mm.

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

To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 0.8 parts by mass of the isocyanate-based crosslinking agent (i) was blended, diluted with toluene, and stirred uniformly to obtain a solid content concentration (active ingredient concentration) of 25 mass parts. % of the pressure-sensitive adhesive composition was prepared.

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

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

Moreover, the adhesive force in 23 degreeC of the 2nd adhesive layer (X2) measured based on the said method was 1.0 N/25 mm.

(1-3) Fabrication of substrate (Y)

100 parts by mass of the solid content of the acrylic urethane resin obtained in Synthesis Example 1, 6.3 parts by mass of the isocyanate-based crosslinking agent (i), 1.4 parts by mass of dioctyltinbis(2-ethylhexanoate) as a catalyst, and the thermally expandable particles A was blended, diluted with toluene, and stirred uniformly to prepare a resin composition having a solid content concentration (active ingredient concentration) of 30% by mass.

In addition, the content of the thermally expandable particles A was 20% by mass relative to the total amount (100% by mass) of the active ingredients in the obtained resin composition.

Then, on the surface of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4100", probe tack value: 0 mN/5 mmφ) having a thickness of 50 µm, which is a non-expandable substrate, 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 substrate layer (Y1) having a thickness of 50 µm.

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

In the above manner, a substrate (Y) composed of an expandable substrate layer (Y1) with a thickness of 50 µm and a non-expandable substrate layer (Y2) with a thickness of 50 µm was produced.

In addition, as a sample for measuring the storage modulus (E') and probe tack value of the intumescent base layer (Y1), the resin composition was applied to the release-treated surface of the easy release film to form a coating film, and the coating film was applied in an atmosphere. It was made to dry at the temperature of 100 degreeC for 120 second, and the expandable base material layer (Y1) of 200 micrometers in thickness was similarly formed.

Then, based on the above-described measurement method, the storage modulus and probe tack value at each temperature of the expandable substrate layer (Y1) were measured. The said measurement result was as follows.

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

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

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

・Probe tack value = 0 mN/5 mmφ

(1-4) Lamination of each layer

While bonding the non-expandable substrate layer (Y2) of the substrate (Y) prepared in the above (1-3) and the second pressure-sensitive adhesive layer (X2) formed in the above (1-2), the expandable substrate layer (Y1 ) and the first pressure-sensitive adhesive layer (X1) formed in the above (1-1) were bonded together.

Then, a support layer formed by laminating in this order an easy release film/second adhesive layer (X2)/non-expandable substrate layer (Y2)/expandable substrate layer (Y1)/first adhesive layer (X1)/heavy release film ( II-A) A sheet for forming was prepared.

Preparation Example 2

(support layer (II-B))

In Production Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles B, and the drying conditions after applying the resin composition to form a coating film were changed to 1 minute at an ambient temperature of 100°C, Production Example In the same manner as in 1, a sheet for forming a support layer (II-B) was produced.

- Thermally expansible particle B: manufactured by Nihon Philite Co., Ltd., product name "031-40DU", expansion start temperature (t) = 80°C.

Preparation Example 3

(supporting layer (II-C))

In Production Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles C, and the drying conditions after coating the resin composition to form a coating film were changed to 1 minute at an ambient temperature of 100°C, Production Example In the same manner as in 1, a sheet for forming a support layer (II-C) was produced.

- Thermally expansible particle C: manufactured by Nihon Philite Co., Ltd., product name "053-40DU", expansion start temperature (t) = 100°C.

In Production Examples 2 and 3, when forming the sheet for forming the support layer (II), the drying temperature after applying the resin composition to form the coating film is set higher than the expansion start temperature (t) of the thermally expandable particles, Since the above drying temperature was the atmospheric temperature, foaming was not observed in the formed support layer (II).

Production Example 4

(supporting layer (II-D))

In Production Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles D, and the drying conditions after coating the resin composition to form a coating film were changed to 1 minute at an ambient temperature of 100°C, Production Example In the same manner as in 1, a sheet for forming a support layer (II-D) was produced.

- Thermally expansible particle D: manufactured by Nihon Philite Co., Ltd., product name "920-40DU", expansion start temperature (t) = 120°C.

[Production of Sheet for Forming Curable Resin Layer (I)]

Preparation Example 5

(Energy ray curable resin layer (I-A))

Each component of the type and compounding amount (both "active ingredient ratio") shown below was blended, further diluted with methyl ethyl ketone, and stirred uniformly to obtain a solution of a curable composition having a solid content concentration (active ingredient concentration) of 61% by mass. prepared.

[Component (a2)]

Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA"): 17.6 parts by mass

[component (b)]

・Acrylic polymer: butyl acrylate (BA) (55 parts by mass), methyl acrylate (MA) (10 parts by mass), glycidyl methacrylate (GMA) (20 parts by mass) and 2-hydroxyethyl acrylate (HEA ) (15 parts by mass) (glass transition temperature: -28°C, Mw: 800,000): 17 parts by mass

[component (c)]

Phenyl 1-hydroxycyclohexyl ketone (manufactured by BASF, product name "IRGACURE-184"): 0.5 part by mass

[component (d)]

- Epoxy group-containing oligomeric silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"): 0.6 parts by mass

[component (e)]

TDI-based crosslinking agent (Toyochem Co., Ltd., product name "BHS-8515"): 0.5 parts by mass

[Component (f)]

・Liquid bisphenol A type epoxy resin (manufactured by Nippon Catalyst Co., Ltd., product name “BPA328”): 16 parts by mass

・Dicyclopentadiene type epoxy resin (manufactured by Nippon Catalyst Co., Ltd., product name "XD-1000L"): 18 parts by mass

Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, product name "HP-7200HH"): 27 parts by mass

・Dicyandiamide (manufactured by ADEKA Co., Ltd., product name "ADEKA VADNA 3636AS"): 1.5 parts by mass

[Component (g)]

・Imidazole (manufactured by Shikoku Kasei Industrial Co., Ltd., product name “2PH-Z”): 1.5 parts by mass

The solution of the curable composition prepared above was applied onto the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes to form an energy ray-curable resin layer (I-A) having a thickness of 25 μm was formed, and a sheet for forming an energy ray curable resin layer (I-A) composed of an energy ray curable resin layer (I-A) and an easy release film was produced.

Preparation Example 6

(Energy ray curable resin layer (I-B))

Each component of the type and compounding amount (both "active ingredient ratio") shown below was blended, further diluted with methyl ethyl ketone, and stirred uniformly to obtain a solution of a curable composition having a solid content concentration (active ingredient concentration) of 61% by mass. prepared.

[Component (a2)]

ε-caprolactone modified tris-(2-acryloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-9300-1CL", trifunctional ultraviolet curable compound): 10 parts by mass

[component (b)]

・Acrylic resin: Acrylic resin obtained by copolymerizing methyl acrylate (MA) (85 parts by mass)/2-hydroxyethyl acrylate (HEA) (15 parts by mass): 28 parts by mass

[component (c)]

2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (manufactured by BASF, product name “Irgacure (registered trademark) 369”): 0.6 parts by mass

[component (d)]

3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name "KBM-503"): 0.4 parts by mass

[component (h)]

・Silica filler (fused quartz filler, average particle diameter of 8 µm): 57 parts by mass

[Component (z)]

32 parts by mass of phthalocyanine-based blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and 50 parts by mass of anthraquinone-based red pigment (Pigment Red 177) are mixed, Pigment obtained by pigmentation so that the total amount of three types of pigments / amount of styrene acrylic resin = 1/3 (mass ratio): 4 parts by mass

The solution of the curable composition prepared above was applied onto the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ° C. for 2 minutes to form an energy ray-curable resin layer (IB) having a thickness of 25 μm was formed, and a sheet for forming an energy ray curable resin layer (I-B) composed of an energy ray curable resin layer (I-B) and an easy release film was produced.

Preparation Example 7

(thermosetting resin layer (I-C))

Each component of the type and amount shown below (both "active ingredient ratio") was blended, further diluted with methyl ethyl ketone, stirred uniformly, and a solution of a curable composition having a solid content concentration (active ingredient concentration) of 61% by mass was prepared.

Acrylic polymer: butyl acrylate (BA) (1 part by mass), methyl acrylate (MA) (74 parts by mass), glycidyl methacrylate (GMA) (15 parts by mass) and 2-hydroxyethyl acrylate (HEA ) (10 parts by mass) (glass transition temperature: 8°C, Mw: 440,000): 18 parts by mass

・Liquid bisphenol A type epoxy resin (manufactured by Nippon Catalyst Co., Ltd., product name “BPA328”): 3 parts by mass

Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "Epicoat 1055"): 20 parts by mass

・Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "XD-1000L"): 1.5 parts by mass

・Dicyandiamide (manufactured by ADEKA, product name “Adeka Badna 3636AS”): 0.5 part by mass

・Imidazole (manufactured by Shikoku Kasei Industrial Co., Ltd., product name “2PH-Z”): 0.5 part by mass

Epoxy group-containing oligomeric silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"): 0.5 parts by mass

Spherical silica filler (manufactured by Admatex Co., Ltd., product name "SC2050MA"): 6 parts by mass

Spherical silica filler (Tatsumori Co., Ltd., product name "SV-10"): 50 parts by mass

The solution of the curable composition prepared above was applied onto the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120° C. for 2 minutes to obtain a thermosetting resin layer (IC) having a thickness of 25 μm. After forming, a sheet for forming a thermosetting resin layer (IC) composed of a thermosetting resin layer (IC) and an easy release film was produced.

[Production of Laminate]

Examples 1 to 5, Reference Example 1

The first pressure-sensitive adhesive layer (X1) exposed by removing the heavy release film of the sheet for forming a support layer (II) shown in Table 1 and the curable resin layer (I) of the sheet for forming a curable resin layer (I) shown in Table 1 The surfaces of were bonded together to obtain a laminate. In Example 5, a product name "Riva Alpha 3195" (expansion start temperature (t) = 170°C) manufactured by Nitto Electric Co., Ltd. was used as the sheet for forming the support layer (II-E).

Table 1 shows the evaluation results of separability and warpage of the laminate obtained in each case.

[Production of cured encapsulation body]

Then, using the laminate obtained in each case, a curing encapsulated body was produced in the following procedure.

(1) Semiconductor chip wit

The easy release film on the side of the support layer (II) of the laminate was removed, and the adhesive surface of the second pressure-sensitive adhesive layer (X2) of the exposed support layer (II) was attached to the support (glass).

Then, the easy release film on the side of the curable resin layer (I) was also removed, and on the surface of the exposed curable resin layer (I), 9 semiconductor chips (each chip size was 6.4 mm × 6.4 mm, chip thickness was 200 [mu]m (#2000)) was placed at necessary intervals so that the back surface on the opposite side to the circuit surface of each semiconductor chip was in contact with the surface of the curable resin layer (I).

(2) formation of cured resin layer (I')

In Examples 1 to 5, after the above (1) and before the following (3), the energy ray curable resin layer (I), which is the curable resin layer (I), was irradiated with ultraviolet (UV) light, and a semiconductor chip was irradiated. A cured resin layer (I') formed by this mounting was formed. In addition, ultraviolet rays were irradiated three times from the support body (glass) side using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Corporation) under conditions of an illuminance of 215 mW/cm 2 and a light amount of 187 mJ/cm 2 .

In Reference Example 1, in (3) described later, without performing (2), the thermosetting resin layer, which is the curable resin layer (I), was cured at the same time in the process of curing the encapsulant.

(3) Formation of curing encapsulation

The surfaces of the nine semiconductor chips and the cured resin layer (I') (thermosetting resin layer in Reference Example 1) at least at the periphery of the semiconductor chip are covered with a thermosetting encapsulating resin film, which is a sealing material, The encapsulating resin film was thermally cured using a vacuum heating and pressing laminator (manufactured by ROHM and HAAS, product name "7024HP5") to prepare a cured encapsulation body. In addition, sealing conditions are as follows.

·Preheating temperature: 100 ℃ for both table and diaphragm

・Vacuum exhaust: 60 seconds

・Dynamic Press Mode: 30 seconds

·Static press mode: 10 seconds

・Enclosure temperature: 180 ℃ × 60 minutes

(4) Separation at the interface (P)

After the above (3), heat expansion treatment is performed for 3 minutes at a temperature of expansion start temperature (t) + 30 ° C. of the thermally expandable particles contained in the support layer (II) of each laminate, and the support layer (II) 1 It separated at the interface (P) of the adhesive layer (X1) and the cured resin layer (I'). Thus, a cured sealed body with a cured resin layer was obtained.

From Table 1, in Examples 1 to 5 using the laminate, which is one aspect of the present invention, warpage did not occur in the formed cured encapsulated body, and the separation of the support layer (II) was excellent.

On the other hand, in Reference Example 1 using a thermosetting resin layer as the curable resin layer, the support layer (II) could not be separated from the cured resin layer (I').

1a, 1b, 2a, 2b, 3: laminated body
(I): Energy ray curable resin layer
(I'): cured resin layer
(II): support layer
(X): pressure-sensitive adhesive layer
(X1): 1st adhesive layer
(X2): 2nd adhesive layer
(Y): description
(Y1): Intumescent substrate layer
(Y2): non-expandable substrate layer
50: support
60: object to be encapsulated (semiconductor chip)
70: sealing material
80: curing encapsulation body
100: cured encapsulation body with cured resin layer
100a: the surface of the curing encapsulation body
110 grinding means
200: redistribution layer
300: external terminal electrode

Claims (11)

an energy ray-curable resin layer (I);
a support layer (II) supporting the energy ray-curable resin layer (I);
The energy ray-curable resin layer (I) has an adhesive surface,
The support layer (II) has a base material (Y) and an adhesive layer (X), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (X) contains thermally expandable particles,
The cured resin layer (I') formed by curing the energy ray-curable resin layer (I) and the support layer (II) are treated to expand the thermally expansible particles, so that the cured resin layer (I') and the support layer (II) ), separated at the interface of the laminate. According to claim 1,
A layered product in which the storage modulus (E') at 23°C of the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) is 1.0 × 10 ⁷ to 1.0 × 10 ¹³ Pa. According to claim 1,
A laminate in which the thickness of the energy ray-curable resin layer (I) is 1 to 500 µm. According to claim 1,
A laminate in which the visible light transmittance of the energy ray-curable resin layer (I) is 5% or more. According to claim 1,
A laminate in which the substrate (Y) has an expandable substrate layer (Y1) containing the thermally expandable particles. According to claim 5,
A layered product in which the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer. According to claim 5,
A laminate formed by directly laminating the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I). According to claim 5,
The base material (Y) has a non-expandable base layer (Y2) and an expandable base layer (Y1),
The support layer (II) has a non-expandable substrate layer (Y2), an expandable substrate layer (Y1), and an adhesive layer (X) in this order,
A laminate formed by directly laminating the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I). According to claim 1,
An object to be sealed is placed on a part of the surface of the energy ray-curable resin layer (I),
The energy ray-curable resin layer (I) is irradiated with energy rays to form a cured resin layer (I′) formed by curing the energy ray-curable resin layer (I);
Covering the surface of the object to be sealed and the cured resin layer (I′) of at least the periphery of the object to be sealed with a thermosetting sealing material;
After thermally curing the encapsulant, the cured resin layer (I′) and the support layer (II) are separated at the interface by a process of expanding the thermally expansible particles to form a cured encapsulant containing the object to be encapsulated. Laminates used to do this. According to claim 9,
Laminate used to prevent warping of the curing encapsulation body. A method for producing a cured sealed body using the laminate according to any one of claims 1 to 10, comprising the following steps (i) to (iv).
Step (i): Step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate
Step (ii): Step of forming a cured resin layer (I′) obtained by curing the energy ray-curable resin layer (I) by irradiating the energy ray-curable resin layer (I) with an energy ray
Step (iii): Covering the surfaces of the object to be sealed and the cured resin layer (I′) at least around the object to be sealed with a thermosetting encapsulant, and curing the encapsulant by heat, including the object to be encapsulated Process of forming cured encapsulation
Step (iv): Step of separating the cured resin layer (I′) and the support layer (II) at the interface by the treatment of expanding the thermally expansible particles to obtain a cured encapsulated body with a cured resin layer

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