JPWO2020070790A1 - Method for manufacturing laminated body and cured sealed body - Google Patents

Abstract

It has an energy ray-curable resin layer (I) and a support layer (II) that supports the energy ray-curable resin layer (I), and the energy ray-curable resin layer (I) has adhesiveness. The support layer (II) has a base material (Y) and a pressure-sensitive adhesive layer, and at least one of the base material (Y) and the pressure-sensitive adhesive layer contains thermosetting particles. A laminate in which a cured resin layer (I') formed by curing an energy ray-curable resin layer (I) and a support layer (II) are separated at an interface by a treatment for expanding the thermosetting particles. Regarding.

Description

The present invention relates to a method for producing a laminated body and a cured sealed body.

In recent years, electronic devices have become smaller, lighter, and more sophisticated, and semiconductor chips may be mounted in packages close to their size. Such a package is sometimes called a CSP (Chip Scale Package). Examples of the CSP include WLP (Wafer Level Package), which processes and completes the final package process with a wafer size, and PLP (Panel Level Package), which processes and completes the package final process with a panel size larger than the wafer size. ..

WLP and PLP are classified into fan-in type and fan-out type. In fan-out type WLP (hereinafter, also referred to as "FOWLP") and PLP (hereinafter, also referred to as "FOPLP"), the semiconductor chip is covered with a sealing material so as to have a region larger than the chip size. The cured encapsulant is formed, and the rewiring layer and the external electrode 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 temporary fixing sheet, a coating step of coating with a thermosetting encapsulant, and thermosetting the encapsulant to cure the encapsulant. A curing step of obtaining a sealed body, a separation step of separating the cured sealed body and a temporary fixing sheet, and a rewiring layer forming step of forming a rewiring layer on the surface of the exposed semiconductor chip side. (Hereinafter, the process performed in the coating process and the curing process is also referred to as "sealing process").

Patent Document 1 discloses a heat-release type pressure-sensitive adhesive sheet for temporary fixing when cutting an electronic component, in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one surface of a base material. In the production of FOWLP and FOPLP, it is also conceivable to use the heat-release type pressure-sensitive adhesive sheet described in Patent Document 1.

Japanese Patent No. 3594853

However, when a cured encapsulant is produced by using the pressure-sensitive adhesive sheet described in Patent Document 1 as a temporary fixing sheet, the cured encapsulant tends to warp due to heat shrinkage. This is because the semiconductor chips sealed in the cured encapsulant are unevenly present on the surface side in contact with the temporary fixing sheet, so that the semiconductor chips having a small coefficient of thermal expansion are present in the cured encapsulant. A region on the side where the ratio is relatively high and a region on the side where the abundance ratio of the cured resin having a large coefficient of thermal expansion is relatively high are generated, and stress is generated due to the difference in the coefficient of thermal shrinkage between the two regions. Conceivable. This problem tends to become more prominent as the package size increases, such as FOWLP and FOPLP.
The warped hardened sealant is likely to crack when the hardened sealant is ground in the next step, for example, and the hardened sealant is hardened and sealed by an arm when the cured sealant is conveyed by an apparatus. There may be adverse effects such as a tendency for problems to occur when the body is handed over.

As a method of suppressing the warp of the cured encapsulant, for example, a method of using a laminated body provided with a temporary fixing layer provided with a thermally expandable adhesive layer containing thermally expandable particles and a thermosetting resin layer is also considered. Be done. That is, the semiconductor chip mounting step and the coating step are carried out on the thermosetting resin layer provided in the laminate, and then the thermosetting resin layer and the sealing material are heat-cured to be cured and sealed with a cured resin layer. This is a method in which after obtaining a stationary body, heat-expandable particles are foamed to separate a cured encapsulant with a cured resin layer and a temporary fixing layer. According to this method, since the cured resin layer functions as a warp prevention layer of the cured encapsulant, a cured encapsulant in which the occurrence of warpage is suppressed can be obtained.

On the other hand, according to the above method, since both the treatment for foaming the heat-expandable particles and the treatment for curing the thermosetting resin layer are heat treatments, the thermosetting resin layer is cured. During the heat treatment for the resin, the heat-expandable particles in the temporary fixing layer may foam. According to the study by the present inventors, if the heat-expandable particles in the temporary fixing layer foam before the thermosetting resin layer is sufficiently cured, the separability of the temporary fixing layer deteriorates in the subsequent separation step. Is known.
Therefore, it is possible to easily separate the cured resin layer and the temporary fixing layer after forming the cured encapsulant with the cured resin layer while imparting the cured resin layer as the warp prevention layer to the cured encapsulant. There is a demand for a laminate that can be used in the production of cured encapsulants.

In view of the above problems, the present invention has a support layer and a curable resin layer, and the object to be sealed can be fixed to the surface of the curable resin layer to perform a sealing process, and the sealing can be performed. A laminated body capable of imparting a cured resin layer as a warp prevention layer to the cured sealed body formed by processing, and the cured resin layer and the support layer can be easily separated, and the laminated body. It is an object of the present invention to provide a method for producing a cured sealed body using the above.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following invention, and have completed the present invention.
That is, the present invention relates to the following [1] to [11].
[1] Energy ray curable resin layer (I) and
It has a support layer (II) that supports the energy ray-curable resin layer (I), and has.
The energy ray curable resin layer (I) has a sticky surface and
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 heat-expandable particles.
A laminate in which a cured resin layer (I') formed by curing an energy ray-curable resin layer (I) and a support layer (II) are separated at an interface by a treatment for expanding the heat-expandable particles.
[2] The storage elastic modulus E'at 23 ° C. of the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) is 1.0 × 10 ^{7 to} 1.0 × 10 ¹³ Pa. The laminated body according to the above [1].
[3] The laminate according to the above [1] or [2], 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 energy ray-curable resin layer (I) has a visible light transmittance of 5% or more.
[5] The laminate according to any one of the above [1] to [4], wherein the base material (Y) has an expandable base material layer (Y1) containing the heat-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 the above [5] or [6], wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.
[8] The base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1).
The support layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X) in this order.
The laminate according to any one of [5] to [7] above, wherein 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).
The object to be sealed and the surface of the cured resin layer (I') at least in the peripheral portion of the object to be sealed are coated 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 the treatment of expanding the thermally expandable particles, and the encapsulating object is separated. The laminate according to any one of the above [1] to [8], which is used for forming a cured encapsulating body containing the mixture.
[10] The laminate according to the above [9], which is used to prevent the cured sealed body from warping.
[11] A method for producing a cured encapsulant using the laminate according to any one of the above [1] to [10], which has the following steps (i) to (iv). Manufacturing method.
Step (i): Place the object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate Step (ii): On the energy ray-curable resin layer (I) Step of irradiating energy rays to form a cured resin layer (I') formed by curing the energy ray-curable resin layer (I) Step (iii): The encapsulation object and the encapsulation object At least the surface of the cured resin layer (I') in the peripheral portion is coated with a thermosetting encapsulant, and the encapsulant is thermosetting to form a cured encapsulant containing the encapsulating object. Step Step (iv): By the treatment of expanding the thermosetting particles, the cured resin layer (I') and the support layer (II) are separated at the interface thereof to obtain a cured sealing body with a cured resin layer. Process

According to the present invention, it has a support layer and a curable resin layer, and an object to be sealed can be fixed to the surface of the curable resin layer to perform a sealing process, and is formed by the sealing process. A laminated body capable of imparting a cured resin layer as a warp prevention layer to the cured sealed body, and the cured resin layer and the support layer can be easily separated, and curing using the laminated body. A method for producing a sealed body can be provided.

It is sectional drawing which shows the structure of the laminated body of the 1st aspect of this invention. It is sectional drawing which shows the structure of the laminated body of the 2nd aspect of this invention. It is sectional drawing which shows the structure of the laminated body of the 3rd aspect of this invention. It is sectional drawing which showed the process of manufacturing the cured encapsulation body with a cured resin layer using the laminated body 1a shown in FIG. 1 (a). It is sectional drawing which shows the processing method of the cured sealing body.

In the present specification, whether or not the target layer is a "non-expandable layer" is determined by the volume change rate calculated from the following formula before and after the treatment for expansion for 3 minutes. If is less than 5%, the layer is considered to be a "non-expandable layer". On the other hand, when the volume change rate is 5% or more, it is determined that the layer is 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
As the "treatment for expansion", for example, in the case of a layer containing the heat-expandable particles, the heat treatment may be performed for 3 minutes at the expansion start temperature (t) of the heat-expandable particles.

As used herein, the term "active ingredient" refers to a component contained in a target composition excluding a diluting solvent.

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

In the present specification, for example, "(meth) acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also used.

In the present specification, the lower limit value and the upper limit value described stepwise for a preferable numerical range (for example, a range such as content) can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". You can also do it.

Unless otherwise specified, each component and material exemplified in the present specification may be used alone or in combination of two or more, and when two or more are used in combination, a combination thereof. And the ratio can be selected arbitrarily.

In the present specification, the "energy ray" means an electromagnetic wave or a charged particle beam having an energy quantum, and examples thereof include ultraviolet rays, radiation, and electron beams. Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light, an LED lamp, or the like as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray curable" means a property of being cured by irradiating with energy rays, and "non-energy ray curable" means a property of not being cured by irradiating with energy rays. do.

[Laminate]
The laminate of one aspect of the present invention has an energy ray-curable resin layer (I) and a support layer (II) that supports 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 a pressure-sensitive adhesive layer (X), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (X) contains heat-expandable particles.

The laminate of one aspect of the present invention is supported by a cured resin layer (I') formed by curing the energy ray-curable resin layer (I) by a treatment of expanding the heat-expandable particles in the support layer (II). Layer (II) can be separated at its interface. That is, in the laminate of one aspect of the present invention, the heat-expandable particles expand by the heat-expansion treatment, and the surface of the layer containing the heat-expandable particles becomes uneven, and the support layer (II) and the energy ray curing The contact area with the cured resin layer (I') formed by curing the sex resin layer (I) is reduced. As a result, at the interface between the support layer (II) and the cured resin layer (I'), they can be easily separated together with a slight force.
Since the laminate of one aspect of the present invention does not need to be heated when the energy ray-curable resin layer (I) is cured, the support layer is used when the energy ray-curable resin layer (I) is cured. The thermosetting particles in (II) do not expand, and the separability between the support layer (II) and the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) is excellent. It becomes a thing.

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 the energy ray-curable resin layer (I) is irradiated with energy rays. , A cured resin layer (I') formed by curing the energy ray-curable resin layer (I) is formed, and the sealed object and the cured resin layer (I') at least in the peripheral portion of the sealing object are formed. The surface of the resin layer (I') and the support layer (II) are coated with a thermosetting encapsulant, the encapsulant is thermally cured, and then the thermosetting particles are expanded. Is preferably used to form a cured encapsulant containing the object to be sealed.
The cured encapsulant formed by the above method is provided with a cured resin layer (I') on the surface on the side where the abundance ratio of the semiconductor chip is relatively high. As a result, the difference in shrinkage stress between the two surfaces of the cured encapsulant can be reduced, and a cured encapsulant whose warpage is effectively suppressed can be obtained.
That is, the laminated body of one aspect of the present invention is useful as a warp prevention laminated body used for preventing the warp of the cured sealing body.
At that time, since the laminate of one aspect of the present invention has an energy ray-curable resin layer (I) that is easier to adjust to increase the adhesive force than the thermosetting resin layer, the object to be sealed is a part of the surface. It can be fixed more securely. Further, when the thermosetting resin layer is heated at a high temperature, it softens mainly in the initial stage of curing, which may cause chip misalignment, whereas the energy ray-curable pressure-sensitive adhesive composition has energy. Since it does not soften when cured by linear irradiation, it is possible to avoid the occurrence of chip misalignment due to curing.

<Structure of laminated body>
Next, the structure of the laminated body of one aspect of the present invention will be described with reference to the drawings.
1 to 3 are schematic cross-sectional views of the laminated body showing the structure of the laminated body of the first to third aspects of the present invention. In the following laminates of the first to third aspects of the present invention, the adhesive surface (that is, the support) of the pressure-sensitive adhesive layer (X) (or the second pressure-sensitive adhesive layer (X2)) to be attached to the support The surface on the opposite side of the surface) and the surface of the energy ray-curable resin layer (I) on the side opposite to the support layer (II) side may be further laminated with a release material.

[Laminate of the first aspect]
Examples of the laminated body of the first aspect of the present invention include the laminated bodies 1a and 1b shown in FIG.
The laminates 1a and 1b include an energy ray-curable resin layer (I) and a support layer (II) having a base material (Y) and an adhesive layer (X), and the base material (Y) and energy. It has a structure in which the linear curable resin layer (I) is directly laminated.
In the laminated body 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 at least one of the heat-expandable particles, and in the laminated body 1a, the base material (Y) contains the heat-expandable particles (expandable base material layer (II). It is a single-layer base material consisting of only Y1).
The base material (Y) may be a single-layered base material composed of only the expandable base material layer (Y1), as in the laminated body 1a shown in FIG. 1 (a), as shown in FIG. 1 (b). Like the laminated body 1b shown, it may be a base material having a multi-layer structure having an expandable base material layer (Y1) and a non-expandable base material layer (Y2). When the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2), the base material (Y) is an expandable base material layer (Y1) and a non-expandable base material layer (Y1). It may consist only of Y2).
Further, it is preferable that the expandable base material layer (Y1) and the non-expandable base material layer (Y2) have a structure in which they are directly laminated.

In the laminate 1a shown in FIG. 1A, the heat-expandable particles contained in the expandable base material layer (Y1) are expanded by the heat-expansion treatment, and the surface of the base material (Y) becomes uneven, resulting in energy. The contact area with the cured resin layer (I') formed by pre-curing the linear curable resin layer (I) is reduced.
At this time, the adhesive surface of the adhesive layer (X) is attached to a support (not shown). When the pressure-sensitive adhesive layer (X) is attached so as to be sufficiently adhered to the support, a force that causes unevenness is generated on the surface of the expandable base material layer (Y1) on the pressure-sensitive adhesive layer (X) side. However, a repulsive force from the adhesive layer (X) is likely to occur. Therefore, it is difficult for irregularities to be formed on the surface of the base material (Y) on the pressure-sensitive adhesive layer (X) side.
As a result, the laminated body 1a can be easily separated at the interface P between the base material (Y) of the support layer (II) and the cured resin layer (I') at once with a slight force.
By forming the pressure-sensitive adhesive layer (X) contained in the laminated body 1a from a pressure-sensitive adhesive composition having a high adhesive force to the support, it is possible to make it easier to separate at the interface P.

From the viewpoint of suppressing the transfer of stress due to the heat-expandable particles to the pressure-sensitive adhesive layer (X) side, the base material (Y) is an expandable group as in the laminated body 1b shown in FIG. 1 (b). It preferably has a material layer (Y1) and a non-expandable base material layer (Y2).
Since the stress due to the expansion of the thermally expandable particles of the expandable base material layer (Y1) is suppressed by the non-expandable base material layer (Y2), it is difficult to be transmitted to the pressure-sensitive adhesive layer (X).
Therefore, unevenness is unlikely to occur on the surface of the pressure-sensitive adhesive layer (X) on the support side, and the adhesion between the pressure-sensitive adhesive layer (X) and the support is almost unchanged before and after the thermal expansion treatment, and good adhesion is maintained. can do. As a result, irregularities are likely to be formed on the surface of the expandable base layer (Y1) on the energy ray-curable resin layer (I) side, and as a result, the support layer (II) is cured with the expandable base layer (Y1). At the interface P with the resin layer (I'), it can be easily separated at once with a slight force.
As in the laminated body 1b shown in FIG. 1B, the expandable base material layer (Y1) and the energy ray-curable resin layer (I) are directly laminated to form the non-expandable base material layer (Y2). It is preferable that the pressure-sensitive adhesive layer (X) is laminated on the surface opposite to the expandable base material layer (Y1).

[Laminate of the second aspect]
Examples of the laminated body of the second aspect of the present invention include the laminated bodies 2a and 2b shown in FIG.
In the laminates 2a and 2b, the pressure-sensitive adhesive layer (X) of the support layer (II) has a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), and the first pressure-sensitive adhesive layer (X1). ) And the second pressure-sensitive adhesive layer (X2) sandwich the base material (Y), 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 laminated body of the second aspect of the present invention, the adhesive surface of the second 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 heat-expandable particles.
The base material (Y) may be a single-layer base material composed of only the expandable base material layer (Y1) as in the laminated body 2a shown in FIG. 2 (a). Like the laminated body 2b shown, it may be a multi-layered base material having an expandable base material layer (Y1) and a non-expandable base material layer (Y2).

However, as described above, as shown in FIG. 2B, the base is formed from the viewpoint of forming a laminated body that maintains good adhesion between the second pressure-sensitive adhesive layer (X2) and the support before and after the thermal expansion treatment. It is preferable that the material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2).
When the base material (Y) having the expandable base material layer (Y1) and the non-expandable base material layer (Y2) is used in the laminated body of the second aspect, it expands as shown in FIG. 2 (b). The first pressure-sensitive adhesive layer (X1) is laminated on the surface of the sex substrate layer (Y1) on the energy ray-curable resin layer (I) side, and the expandable substrate layer of the non-expandable substrate layer (Y2). It is preferable to have a structure in which the second pressure-sensitive adhesive layer (X2) is laminated on the surface opposite to (Y1).

In the laminated body of the second aspect, the heat-expandable particles in the expandable base material layer (Y1) constituting the base material (Y) are expanded by the heat expansion treatment, and the surface of the expandable base material layer (Y1) is expanded. Unevenness occurs.
Then, the first pressure-sensitive adhesive layer (X1) is also pushed up by the unevenness generated on the surface of the expandable base material layer (Y1), and the unevenness is also formed on the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (X1). 1 The contact area between the pressure-sensitive adhesive layer (X1) and the cured resin layer (I') formed by pre-curing the energy ray-curable resin layer (I) is reduced. As a result, the interface P between the first pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I') can be easily separated at once with a slight force.
In the laminate of the second aspect of the present invention, the base material (Y) of the support layer (II) expands from the viewpoint of forming a laminate that can be easily separated at the interface P with a smaller force. It is preferable that the sex base material layer (Y1) and the first pressure-sensitive adhesive layer (X1) are directly laminated.

[Laminate of the third aspect]
Examples of the laminated body of the third aspect of the present invention include the laminated body 3 shown in FIG.
The laminate 3 shown in FIG. 3 has a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing heat-expandable particles, on one surface side of the base material (Y), and is a base material (X1). A support layer (II) having a second pressure-sensitive adhesive layer (X2), which is a non-expandable pressure-sensitive adhesive layer, is provided on the other surface side of Y), and the first pressure-sensitive adhesive layer (X1) and an energy ray-curable resin layer are provided. It has a structure in which (I) and (I) are directly laminated.
In the laminated body 3, the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown).
The base material (Y) contained in the laminate of the third aspect of the present invention is preferably composed of a non-expandable base material layer.

In the laminate of the third aspect of the present invention, the heat-expandable particles in the first pressure-sensitive adhesive layer (X1), which is the expandable pressure-sensitive adhesive layer, expand by the heat expansion treatment, and the first pressure-sensitive adhesive layer (X1) The surface becomes uneven, and the contact area between the first pressure-sensitive adhesive layer (X1) and the cured resin layer (I') formed by pre-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 base material (Y) side, unevenness is unlikely to occur.
Therefore, the heat expansion treatment tends to form irregularities on the surface of the first pressure-sensitive adhesive layer (X1) on the energy ray-curable resin layer (I) side, and as a result, the first pressure-sensitive adhesive layer of the support layer (II) ( At the interface P between X1) and the cured resin layer (I'), it can be easily separated 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), and may consist of the support layer (II) and the energy ray-curable resin layer (I). It may have other layers other than the above. Examples of other layers include an adhesive layer provided on the surface of the energy ray-curable resin layer (I) opposite to the support layer (II).
Further, the laminate of one aspect of the present invention preferably does not have a thermosetting resin layer from the viewpoint that heating is not required as much as possible in steps other than the heat expansion treatment. However, the thermosetting resin layer here means a layer having thermosetting property and non-energy ray curable property.

<Various physical characteristics of laminated body>
(Peeling force (F ₀ ))
Before the energy ray-curable resin layer (I) is cured and before the heat expansion treatment, the support layer (II) and the support layer (II) are used from the viewpoint of sufficiently fixing the object to be sealed so as not to adversely affect the sealing operation. It is preferable that the adhesion to the energy ray-curable resin layer (I) 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 heat expansion treatment is performed. _{The peeling force (F 0} ) at the time of separation at the interface P with is preferably 100 mN / 25 mm or more, more preferably 130 mN / 25 mm or more, further preferably 160 mN / 25 mm or more, and preferably 50,000 mN / 25 mm or more. It is as follows.
The peeling force (F ₀ ) is a value measured by the following measuring method.
<Measurement of peeling force (F _0)>
After allowing the laminate to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name "PL Thin") is applied to the surface of the energy ray-curable resin layer (I). ") Is affixed.
Next, the support layer (II) side of the laminate is attached to a glass plate (manufactured by Yukou Shokai Co., Ltd., float plate glass, 3 mm (JISR 3202 product)) via an adhesive. Next, the end portion of the glass plate to which the laminate is attached is fixed to the lower chuck of a universal tensile tester (manufactured by Orient Tech Co., Ltd., product name "Tencilon 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 be peeled off at the interface P between the support layer (II) of the laminated body and the energy ray-curable resin layer (I). .. Then, under the same environment as above, the peeling force measured when peeling at the interface P at a tensile speed of 300 mm / min by the 180 ° peeling method based on JIS Z 0237: 2000 is referred to as "peeling force (F _0). ) ”.

(Peeling force (F ₁ ))
In the laminate of one aspect of the present invention, the energy ray-curable resin layer (I) is cured to form a cured resin layer (I'), and then the support layer (II) and the cured resin layer (I) are subjected to heat expansion treatment. _{The peeling force (F 1} ) at the interface P with') is usually 2000 mN / 25 mm or less, preferably 1000 mN / from the viewpoint of enabling easy separation at the interface P with a slight force. It is 25 mm or less, more preferably 500 mN / 25 mm or less, more preferably 150 mN / 25 mm or less, still more preferably 100 mN / 25 mm or less, still more preferably 50 mN / 25 mm or less, and most preferably 0 mN / 25 mm.
When the peeling force (F ₁ ) is 0 mN / 25 mm, even if an attempt is made to measure the peeling force, the peeling force may be too small to be measured.
The peeling force (F ₁ ) is a value measured by the following measuring method.
<Measurement of peeling force (F _1)>
After allowing the laminate to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), an adhesive tape (manufactured by Lintec Corporation, product name) is applied to the surface of the energy ray-curable resin layer (I) of the laminate. "PL Shin") is attached.
Next, the support layer (II) side of the laminate is attached to a glass plate (manufactured by Yukou Shokai Co., Ltd., float plate glass, 3 mm (JIS R 3202 product)) via an adhesive.
Next, ultraviolet rays are irradiated three times under the conditions of an illuminance of 215 mW / cm ² and a light intensity of 187 mJ / cm ² to cure the energy ray-curable resin layer (I) to form a cured resin layer (I'). Then, 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 base material layer (Y1) of the laminate. After that, in the same _{manner as the above-mentioned measurement of the peeling force (F 0} ), the peeling force measured at the interface P between the support layer (II) and the cured resin layer (I') under the above conditions is measured. Let it be "peeling force (F ₁ )".
In the measurement of the peeling force (F ₁ ), when the support layer (II) of the laminated body was to be fixed by the upper chuck of the universal tensile tester, the cured resin layer (I') was completely separated at the interface P. If it 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 the adhesive layer (X))
In the laminate of one aspect of the present invention, 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.). The adhesive strength is preferably 0.1 to 10.0 N / 25 mm, more preferably 0.2 to 8.0 N / 25 mm, still more preferably 0.4 to 6.0 N / 25 mm, still more preferably 0.5. It is ~ 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 strengths of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are different, respectively. The above range is preferable, but from the viewpoint of improving the adhesion to the support and making it easier to separate all at once at the interface P, the second pressure-sensitive adhesive layer (X2) to be attached to the support It is more preferable that the adhesive strength is higher than the adhesive strength of the first pressure-sensitive adhesive layer (X1).

(Adhesive strength of energy ray curable resin layer (I))
In the laminated body of one aspect of the present invention, the energy ray-curable resin layer (I) is the surface on the side on which the object to be sealed is placed (that is, that is, from the viewpoint of improving the adhesion to the object to be sealed. The surface opposite to the support layer (II)) is sticky.
Specifically, the adhesive strength of the surface of the energy ray-curable resin layer (I) on the side on which the object to be sealed is placed at room temperature (23 ° C.) is from the viewpoint of sufficiently fixing the object to be sealed. It is preferably 0.05 N / 25 mm or more, more preferably 0.10 N / 25 mm or more, and further 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, 40 N / 25 mm or less, or 30 N / 25 mm or less.

In this specification, these adhesive strengths are values measured by the following measuring methods.
<Measurement of adhesive strength>
A PET film having a thickness of 50 μm (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”) is laminated on the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) formed on the release film.
Then, the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) is attached to a stainless steel plate (SUS304 No. 360 polishing) as an adherend, and the temperature is 23 ° C. and 50% RH (relative humidity). After allowing to stand for 24 hours in an environment, the adhesive strength at 23 ° C. is measured at a tensile speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000 under the same environment.

(Probe tack value of base material (Y))
The base material (Y) contained in the support layer (II) is a non-adhesive base material.
In one aspect of the present invention, it is determined whether or not the substrate is a non-adhesive substrate when the probe tack value measured in accordance with JISZ 0237: 1991 with respect to the surface of the substrate of interest is less than 50 mN / 5 mmφ. If there is, the base material is judged to be a "non-adhesive base material". On the other hand, if the probe tack value is 50 mN / 5 mmφ or more, the base material is judged to be an “adhesive base material”.
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, more preferably less than 10 mN / 5 mmφ. More preferably, it is less than 5 mN / 5 mmφ.
The probe tack value on the surface of the base material (Y) is a value measured by the following measuring method.
<Measurement of probe tack value>
A test sample is prepared by cutting a base material to be measured into a square having a side of 10 mm and then allowing it to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity). In an environment of 23 ° C. and 50% RH (relative humidity), use a tacking tester (manufactured by Nippon Special Instruments Co., Ltd., product name "NTS-4800") to determine the probe tack value on the surface of the test sample. Measured according to Z0237: 1991. Specifically, a stainless steel probe having a diameter of 5 mm ^{is brought into contact with the surface of the test sample for 1 second with a contact load of 0.98 N / cm 2} , and then the probe is brought into contact with the surface of the test sample at a speed of 10 mm / sec. The force required to separate from the surface is measured, and the obtained value is used as the probe tack value of the test sample.

Next, each layer constituting the laminated body of one aspect of the present invention will be described.

<Support layer (II)>
The support layer (II) included in the laminate of one aspect 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) is It contains heat-expandable particles. As described above, the support layer (II) is a layer separated from the energy ray-curable resin layer (I), which is the object to be supported, by the thermal expansion treatment, and is a layer that plays a role as a so-called temporary fixing layer. ..
The support layer (II) used in one aspect of the present invention depending on whether the layer containing the heat-expandable particles is included in the structure of the base material (Y) or the structure of the pressure-sensitive adhesive layer (X). Can be divided into the following aspects.
-Support layer (II) of the first aspect: A support layer (II) including a base material (Y) having an expandable base material 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 heat-expandable particles, and a non-expandable pressure-sensitive adhesive on both sides of the base material (Y). A support layer (II) having a second pressure-sensitive adhesive layer (X2) which is a layer.

[Support layer of the first aspect (II)]
As the support layer (II) of the first aspect, as shown in FIGS. 1 and 2, the base material (Y) has an expandable base material layer (Y1) containing heat-expandable particles.
In the support layer (II) of the first aspect, the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer from the viewpoint that it can be easily separated collectively at the interface P with a slight force.
Specifically, in the support layer (II) of the laminates 1a and 1b shown in FIG. 1, the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer.
Further, in the support layer (II) of the laminates 2a and 2b shown in FIG. 2, both the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are non-expandable pressure-sensitive adhesive layers. It is preferable to have.
Since the base material (Y) has the expandable base material layer (Y1) as in the support layer (II) of the first aspect, the pressure-sensitive adhesive layer (X) does not need to have expandability, and the base material (X) does not need to have expandability. Not constrained by the composition, composition and process for granting. This makes it possible to design the pressure-sensitive adhesive layer (X) by giving priority to desired performance other than expandability, such as performance such as adhesiveness, productivity, and economy. The degree of freedom in design of (X) can be improved.

The thickness of the base material (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 30. It is ~ 300 μm.

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

In the present specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of pressure-sensitive adhesive layers (X), the above-mentioned "thickness of the pressure-sensitive adhesive layer (X)" is determined. It means the thickness of each 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)).
Further, in the present specification, the thickness of each layer constituting the laminated body means a value measured by the method described in the examples.

In the support layer (II) of the first aspect, the thickness ratio [(Y1) / (X)] of the expandable base material layer (Y1) and the pressure-sensitive adhesive layer (X) before the thermal expansion treatment is defined as It is preferably 1000 or less, more preferably 200 or less, still more preferably 60 or less, and even more preferably 30 or less.
When the thickness ratio is 1000 or less, the laminate can be easily separated at the interface P between the support layer (II) and the cured resin layer (I') by heat expansion treatment with a slight force. can do.
The thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and even more preferably 5.0 or more.

Further, in the support layer (II) of the first aspect, the base material (Y) may be composed of only the expandable base material layer (Y1) as shown in FIG. 1 (a). As shown in FIG. 1 (b), the energy ray-curable resin layer (I) side has an expandable base material layer (Y1), and the adhesive layer (X) side has a non-expandable base material layer (Y2). It may have.

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

[Support layer of the second aspect (II)]
As the support layer (II) of the second aspect, as shown in FIG. 3, a first pressure-sensitive adhesive layer which is an expandable pressure-sensitive adhesive layer containing heat-expandable particles on both side surfaces of the base material (Y), respectively. Examples thereof include those having (X1) and a second pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer.
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 with each other.
In the support layer (II) of the second aspect, the base material (Y) is preferably a non-expandable base material. The non-expandable base material is preferably composed of only the non-expandable base material layer (Y2).

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 second pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer before the heat expansion treatment. The thickness ratio [(X1) / (X2)] with and is preferably 0.1 to 80, more preferably 0.3 to 50, and even more preferably 0.5 to 15.

Further, 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, and the base material (Y) before the thermal expansion treatment [(X1). / (Y)] is preferably 0.05 to 20, more preferably 0.1 to 10, and even more preferably 0.2 to 3.

Hereinafter, the thermally expandable particles contained in any of the layers constituting the support layer (II) will be described, and then the expandable base material layer (Y1) and the non-expandable base material constituting the base material (Y) will be described. The layer (Y2) and the pressure-sensitive adhesive layer (X) will be described in detail.

[Thermal expandable 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 size of the thermally expandable particles used in one embodiment of the present invention before expansion at 23 ° C. is preferably 3 to 100 μm, more preferably 4 to 70 μm, still more preferably 6 to 60 μm, still more preferably 10 to 10. It is 50 μm.
The average particle size of the heat-expandable particles before expansion is the volume medium particle size (D ₅₀ ), and is a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name “Mastersizer 3000”). In the particle distribution of the heat-expandable particles before expansion measured using the above, it means the particle size in which the cumulative volume frequency calculated from the smaller particle size of the heat-expandable particles before expansion corresponds to 50%.

_{The 90% particle size (D 90} ) of the heat-expandable particles used in one embodiment of the present invention before expansion at 23 ° C. is preferably 10 to 150 μm, more preferably 20 to 100 μm, still more preferably 25 to 90 μm. Even more preferably, it is 30 to 80 μm.
_{The 90% particle size (D 90} ) of the thermally expandable particles before expansion is the expansion measured using a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name "Mastersizer 3000"). In the particle distribution of the previous heat-expandable particles, it means the particle size in which the cumulative volume frequency calculated from the smaller particle size of the heat-expandable particles before expansion corresponds to 90%.

The thermally expandable particles used in one embodiment of the present invention may be particles having an expansion start temperature (t) higher than the curing temperature of the encapsulant, which does not expand when the encapsulant is cured. Is preferably a thermally expandable particle whose expansion start temperature (t) is adjusted to 60 to 270 ° C. The expansion start temperature (t) is appropriately selected according to the curing temperature of the sealing material to be used.
Further, in the present specification, the expansion start temperature (t) of the thermally expandable particles means a value measured based on the method described in the examples.

The heat-expandable particles are microencapsulated foaming agents composed of an outer shell made of a thermoplastic resin and an contained component contained in the outer shell and vaporized when heated to a predetermined temperature. It is preferable to have.
Examples of the thermoplastic resin constituting the outer shell of the microencapsulating foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone and the like.

Examples of the contained components contained in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptan, isooctane, isononan, isodecane, cyclopropane, cyclobutane, and cyclopentane. , Cyclohexane, cycloheptan, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, isotoridecan, 4-methyldodecane, isotetradecane, isopentadecane, iso Hexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isonanodecane, 2,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane , Cyclopentadecane, nonylcyclohexane, decylcyclohexane, pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane and the like.
These inclusion components may be used alone or in combination of two or more.
The expansion start temperature (t) of the heat-expandable particles can be adjusted by appropriately selecting the type of the inclusion component.

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

<Expandable base material layer (Y1)>
The expandable base material layer (Y1) contained in the support layer (II) used in one aspect of the present invention is a layer containing thermally expandable particles and capable of expanding by a predetermined thermal expansion treatment.

From the viewpoint of improving the interlayer adhesion between the expandable base material layer (Y1) and other layers to be laminated, the surface of the expandable base material layer (Y1) is subjected to an oxidation method, an unevenness method, or the like. Treatment, easy adhesion treatment, or primer treatment may be performed.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, and examples of the unevenness method include a sandblast method and a solvent treatment method. And so on.

In one aspect of the present invention, the expandable base material layer (Y1) preferably satisfies the following requirement (1).
- Requirement (1): in the expansion starting temperature (t) of the thermal expandable particles, the storage elastic modulus E of the expandable substrate layer (Y1) '(t) is less than or equal to 1.0 × ¹⁰ 7 Pa.
In the present specification, the storage elastic modulus E'of the expandable base 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 showing the rigidity of the expandable base material layer (Y1) immediately before the thermally expandable particles expand.
In order to enable easy separation at the interface P between the support layer (II) and the cured resin layer (I') with a slight force, the support layer ( It is necessary to facilitate the formation of irregularities on the surface on the side where the energy ray-curable resin layer (I) of II) is laminated.
That is, in the expandable base material layer (Y1) that satisfies the above requirement (1), the heat-expandable particles expand at the expansion start temperature (t) and become sufficiently large, and the energy ray-curable resin layer (I) is laminated. Unevenness is likely to be formed on the surface of the support layer (II) on the side of the surface.
As a result, it can be a laminate that can be easily separated with a slight force at the interface P between the support layer (II) and the cured resin layer (I').

From the above viewpoint, the storage elastic modulus E'(t) of the expandable base layer (Y1) specified in the requirement (1) is preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 × 10. ^{It is 6} Pa or less, more preferably 6.0 × 10 ⁶ Pa or less, and even more preferably 4.0 × 10 ⁶ Pa or less.
In addition, the flow of expanded heat-expandable particles is suppressed, and the shape-retaining property of the unevenness formed on the surface of the support layer (II) on the side where the energy ray-curable resin layer (I) is laminated is improved. From the viewpoint of making it easier to separate at the interface P with a slight force, the storage elastic modulus E'(t) of the expansive substrate layer (Y1) specified in the requirement (1) is preferably 1.0 ×. It is 10 ³ Pa or more, more preferably 1.0 × 10 ⁴ Pa or more, and further preferably 1.0 × 10 ⁵ Pa or more.

The expandable base material layer (Y1) is preferably formed from the resin composition (y) containing the resin and the heat-expandable particles.
The resin composition (y) may contain an additive for a base material, if necessary, as long as the effects of the present invention are not impaired.
Examples of the base material additive include a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an anti-blocking agent, a colorant and the like.
These base material additives may be used alone or in combination of two or more.
When these base material additives are contained, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the resin. It is 10 parts by mass.

The content of the heat-expandable particles is preferably 1 to 40 with respect to the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the active ingredient of the resin composition (y). It is by mass, more preferably 5 to 35% by mass, still more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass.

The resin contained in the resin composition (y), which is the material for forming the expandable base material layer (Y1), may be a non-adhesive resin or an adhesive resin.
That is, even if the resin contained in the resin composition (y) is an adhesive resin, the adhesive resin is polymerizable in the process of forming the expandable base material layer (Y1) from the resin composition (y). It suffices that the resin obtained by polymerizing with the compound becomes a non-adhesive resin, and the expandable base material layer (Y1) containing the resin becomes non-adhesive.

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

When the resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and any of a block copolymer, a random copolymer, and a graft copolymer is used. It may be.

The content of the resin is preferably 50 to 99% by mass with respect to the total amount (100% by mass) of the expandable base material layer (Y1) or the total amount (100% by mass) of the active ingredient of the resin composition (y). , More preferably 60 to 95% by mass, still more preferably 65 to 90% by mass, and even more preferably 70 to 85% by mass.

From the viewpoint of forming the expandable base material layer (Y1) satisfying the above requirement (1), the resin contained in the resin composition (y) is selected from acrylic urethane-based resin and olefin-based resin1. It preferably contains more than a seed.
Further, as the acrylic urethane resin, the following resin (U1) is preferable.
-Acrylic urethane resin (U1) obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing a (meth) acrylic acid ester.

(Acrylic urethane resin (U1))
Examples of the urethane prepolymer (UP) that serves as the main chain of the acrylic urethane resin (U1) include a reaction product of a polyol and a polyhydric isocyanate.
The urethane prepolymer (UP) is preferably obtained by further performing a chain extension reaction using a chain extender.

Examples of polyols used as raw materials for urethane prepolymers (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 alone or in combination of two or more.
As the polyol used in one embodiment of the present invention, diols are preferable, ester-type diols, alkylene-type diols and carbonate-type diols are more preferable, and ester-type diols and carbonate-type diols are even more preferable.

Examples of the ester-type diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol; ethylene glycol, propylene glycol, and the like. One or more selected from diols such as diethylene glycol and alkylene glycol such as dipropylene glycol; and phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4 , 4'-dicarboxylic 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, hexa Examples thereof include dicarboxylic acids such as hydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and methylhexahydrophthalic acid, and one or more selected from these anhydrides.
Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butyrene adipate diol, polybutylene hexamethylene adipate diol, Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol and polyneo Examples thereof include pentyl terephthalate diol.

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; ethylene glycol, propylene glycol, and the like. Examples thereof include alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; and polyoxyalkylene glycols such as polytetramethylene glycol.

Examples of the carbonate type 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 and the like.

Examples of the polyisocyanate used as a raw material for the urethane prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
These polyvalent isocyanates may be used alone or in combination of two or more.
Further, these polyvalent isocyanates may be a trimethylolpropane adduct-type modified product, a biuret-type modified product reacted with water, or an isocyanurate-type modified product containing an isocyanurate ring.

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

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexane. Examples thereof include diisocyanate, methyl-2,4-cyclohexanediisocyanate and methyl-2,6-cyclohexanediisocyanate, but 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 a reaction product of a diol and a diisocyanate, and is a straight chain having ethylenically unsaturated groups at both ends. Urethane prepolymers are preferred.
As a method of introducing an ethylenically unsaturated group into both ends of the linear urethane prepolymer, an NCO group at the terminal of the linear urethane prepolymer formed by reacting a diol and a diisocyanate compound and a hydroxyalkyl (meth) acrylate are used. There is a method of reacting with.

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

The vinyl compound that forms the side chain of the acrylic urethane resin (U1) contains at least a (meth) acrylic acid ester.
As the (meth) acrylic acid ester, one or more selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is preferable, and alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are more preferably used in combination.

When alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are used in combination, the mixing ratio of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass. It is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and even more preferably 1.5 to 10 parts by mass.

The alkyl group of the alkyl (meth) acrylate has preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms.

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

Examples of vinyl compounds other than (meth) acrylic acid ester include aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate. , (Meta) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, polar group-containing monomers such as meta (acrylamide); and the like.
These may be used alone or in combination of two or more.

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 to 100% by mass, more preferably 90 to 100% by mass.

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

In the acrylic urethane 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)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, and even more preferably 35 in terms of mass ratio. / 65-55 / 45.

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

Specific olefinic resins, for example, ultra low density polyethylene (VLDPE, density: 880 kg / ^{m 3} or more 910 kg / ^m less than ^3), low density polyethylene (LDPE, density: 910 kg / ^{m 3} or more 915 kg / ^m less than ³ ), Medium density polyethylene (MDPE, density: 915 kg / m ³ or more and less than 942 kg / m ³ ), high density polyethylene (HDPE, density: 942 kg / m ³ or more), linear low density polyethylene and other polyethylene resins; polypropylene resin (PP); Polybutene resin (PB); Ethylene-propylene copolymer; Olefin-based elastomer (TPO); Poly (4-methyl-1-pentene) (PMP); Ethethylene-vinyl acetate copolymer (EVA); Polyethylene- Vinyl alcohol copolymer (EVOH); olefin-based ternary copolymer such as ethylene-propylene- (5-ethylidene-2-norbornene); and the like.

In one aspect of the present invention, the olefin resin may be a modified olefin resin further subjected to one or more modifications selected from acid modification, hydroxyl group modification, and acrylic modification.

For example, the acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin is a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof with the above-mentioned non-modified olefin-based resin. Can be mentioned.
Examples of the unsaturated carboxylic acid or its anhydride include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, and itaconic anhydride. , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornendicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like.
The unsaturated carboxylic acid or its anhydride may be used alone or in combination of two or more.

The acrylic-modified olefin-based resin obtained by subjecting the olefin-based resin to acrylic modification is a modification obtained by graft-polymerizing the above-mentioned non-modified olefin-based resin, which is the main chain, with an alkyl (meth) acrylate as a side chain. Examples include polymers.
The alkyl group of the above alkyl (meth) acrylate has preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and further preferably 1 to 12 carbon atoms.
Examples of the above-mentioned alkyl (meth) acrylate include the same compounds as those that can be selected as the monomer (a1') described later.

Examples of the hydroxyl group-modified olefin resin obtained by subjecting the olefin resin to hydroxyl group modification include a modified polymer obtained by graft-polymerizing a hydroxyl group-containing compound on the above-mentioned non-modified olefin resin which is the main chain.
Examples of the hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. Hydroxyalkyl (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol can be mentioned.

(Resin other than acrylic urethane resin and olefin resin)
In one aspect of the present invention, the resin composition (y) may contain a resin other than the acrylic urethane resin and the olefin resin as long as the effects of the present invention are not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene co-weight. Combined; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resin; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; Fluorine-based resin and the like can be mentioned.

However, from the viewpoint of forming the expandable base material layer (Y1) satisfying the above requirement (1), the content ratio of the resin other than the acrylic urethane resin and the olefin resin in the resin composition (y) is smaller. preferable.
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 20 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). It is less than 10 parts by mass, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, and even more preferably less than 1 part by mass.

(Solvent-free resin composition (y1))
As the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray-polymerizable monomer, and the above-mentioned heat-expandable particles are blended. Therefore, a solvent-free resin composition (y1) that does not contain a solvent can be mentioned.
In the solvent-free resin composition (y1), no solvent is blended, but the energy ray-polymerizable monomer contributes to the improvement of the plasticity of the oligomer.
By irradiating the coating film formed from the solvent-free resin composition (y1) with energy rays, it is easy to form an expandable base material layer (Y1) that satisfies the above requirement (1).

The types, shapes, and blending amounts (contents) of the heat-expandable particles blended in the solvent-free resin composition (y1) are as described above.

The mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1000 to 50,000, more preferably 2000 to 40,000, still more preferably 3000 to 35,000. Even more preferably, it is 4000 to 30000.

The oligomer may be any resin contained in the above-mentioned resin composition (y) having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less. UP) is preferable.
As the oligomer, a modified olefin resin having an ethylenically unsaturated group can also be used.

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

Examples of the energy ray-polymerizable monomer include isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, and adamantan (adamantan). Alicyclic polymerizable compounds such as meta) acrylates and tricyclodecane acrylates; aromatic polymerizable compounds such as phenylhydroxypropyl acrylates, benzyl acrylates and phenolethylene oxide modified acrylates; tetrahydrofurfuryl (meth) acrylates, morpholine acrylates, N- Examples thereof include heterocyclic polymerizable compounds such as vinylpyrrolidone and N-vinylcaprolactam.
These energy ray-polymerizable monomers may be used alone or in combination of two or more.

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

In one aspect of the present invention, the solvent-free resin composition (y1) is preferably further blended with a photopolymerization initiator.
By containing the photopolymerization initiator, the curing reaction can be sufficiently advanced even by irradiation with relatively low-energy energy rays.

Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfate, tetramethylthium monosulfide, and azobisisobutyrol. Examples thereof include nitrile, dibenzyl, diacetyl, 8-chloranthraquinone and the like.
These photopolymerization initiators may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, and further, based on the total amount (100 parts by mass) of the above-mentioned oligomer and energy ray-polymerizable monomer. It is preferably 0.02 to 3 parts by mass.

<Non-expandable base material layer (Y2)>
Examples of the material for forming the non-expandable base material layer (Y2) constituting the base material (Y) include paper materials, resins, metals, and the like, which are appropriately used according to the use of the laminate according to one aspect of the present invention. You can choose.

Examples of the paper material include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfate paper, glassin paper and the like.
Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyethylene terephthalate and poly. Polyester resins such as butylene 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; Polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; fluorine resin and the like can be mentioned.
Examples of the metal include aluminum, tin, chromium, titanium and the like.

These forming materials may be composed of one kind, or two or more kinds may be used in combination.
As the non-expandable base material layer (Y2) in which two or more kinds of forming materials are used in combination, a paper material laminated with a thermoplastic resin such as polyethylene, a resin film containing the resin, or a metal film formed on the surface of the sheet. And so on.
As a method for forming the metal layer, for example, a method of vapor-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 by using a general pressure-sensitive adhesive. The method of doing this can be mentioned.

Here, in one aspect of the present invention, when the expandable particles contained in the expandable base material layer (Y1) expand, the non-expandable base material layer (Y2) side of the expandable base material layer (Y1) From the viewpoint of suppressing the formation of irregularities on the surface and predominantly forming irregularities on the surface of the expansive substrate layer (Y1) on the pressure-sensitive adhesive layer (X1) side, the non-expandable substrate layer ( It is preferable that Y2) has a rigidity that does not deform due to the expansion of the expandable particles. Specifically, at a temperature (t) expansion at the start of expandable particles, storage modulus E of the non-expandable base layer (Y2) '(t) is at 1.1 × 10 7 ^Pa or higher Is preferable.

When the non-expandable substrate layer (Y2) contains a resin, the non-expandable substrate layer is formed from the viewpoint of improving the interlayer adhesion between the non-expandable substrate layer (Y2) and other layers to be laminated. Similar to the above-mentioned expandable base material layer (Y1), the surface of (Y2) may be subjected to surface treatment by an oxidation method, an unevenness method or the like, easy adhesion treatment, or primer treatment.

When the non-expandable base material layer (Y2) contains a resin, the above-mentioned base material additive that can be contained in the resin composition (y) may be contained together with the resin.

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

Further, the non-expandable base material 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 base material layer (Y2), it is possible to adjust the volume change rate within the above range even if the heat-expandable particles are contained.
However, it is preferable that the non-expandable base material layer (Y2) does not contain thermally expandable particles. When the non-expandable base material layer (Y2) contains the heat-expandable particles, the smaller the content is, the more preferable, and the specific content of the heat-expandable particles is the non-expandable base material layer (Y2). 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 0. It is less than 001% by mass.

<Adhesive layer (X)>
The pressure-sensitive adhesive layer (X) included in the support layer (II) used in one aspect of the present invention can be formed from the pressure-sensitive adhesive composition (x) containing a pressure-sensitive adhesive resin.
Further, the pressure-sensitive adhesive composition (x) may contain an additive for a pressure-sensitive adhesive such as a cross-linking agent, a pressure-sensitive adhesive, a polymerizable compound, and a polymerization initiator, if necessary.
Hereinafter, each component contained in the pressure-sensitive adhesive composition (x) will be described.
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 included. , Can be formed from the pressure-sensitive adhesive composition (x) containing each of the following components.

(Adhesive resin)
The adhesive resin used in one embodiment of the present invention is preferably a polymer having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
The mass average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and further preferably 30,000 from the viewpoint of improving the adhesive strength. ~ 1 million.

Specific examples of the adhesive resin include rubber resins such as acrylic resins, urethane resins and polyisobutylene resins, polyester resins, olefin resins, silicone resins and polyvinyl ether resins.
These adhesive resins may be used alone or in combination of two or more.
When these adhesive resins are copolymers having two or more kinds of constituent units, the form of the copolymer is not particularly limited, and the block copolymer, the random copolymer, and the graft are used together. It may be any of the polymers.

In one aspect of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
When the support layer (II) having the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is used, the first pressure-sensitive adhesive layer (I) in contact with the energy ray-curable resin layer (I) ( Since the acrylic resin is contained in X1), 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 30 to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x) or the adhesive layer (X). It is 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass.

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

(Crosslinking agent)
In one aspect of the present invention, when the pressure-sensitive adhesive composition (x) contains a pressure-sensitive adhesive resin having a functional group, it is preferable that the pressure-sensitive adhesive composition (x) further contains a cross-linking agent.
The cross-linking agent reacts with a pressure-sensitive adhesive resin having a functional group to cross-link the pressure-sensitive adhesive resins using the functional group as a cross-linking starting point.

Examples of the cross-linking agent include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, and a metal chelate-based cross-linking agent.
These cross-linking agents may be used alone or in combination of two or more.
Among these cross-linking agents, isocyanate-based cross-linking agents are preferable from the viewpoint of increasing the cohesive force to improve the adhesive force and the availability.

The content of the cross-linking agent is appropriately adjusted according to the number of functional groups of the adhesive resin, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having functional groups. It is more preferably 0.03 to 7 parts by mass, and further preferably 0.05 to 5 parts by mass.

(Adhesive)
In one aspect of the present invention, the pressure-sensitive adhesive composition (x) may further contain a pressure-sensitive adhesive from the viewpoint of further improving the pressure-sensitive adhesive strength.
In the present specification, the "adhesive-imparting agent" refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, which is a component that supplementarily improves the adhesive strength of the above-mentioned adhesive resin, and refers to the above-mentioned adhesion. It is distinguished from the sex resin.
The mass average molecular weight (Mw) of the tackifier is preferably 400 to 9000, more preferably 500 to 8000, and even more preferably 800 to 5000.

As the tackifier, for example, it is obtained by copolymerizing a C5 distillate such as rosin-based resin, terpene-based resin, styrene-based resin, penten, isoprene, piperin, and 1,3-pentadien produced by thermal decomposition of petroleum naphtha. Examples thereof include C5 petroleum resins obtained by copolymerizing C9 petroleum resins such as inden produced by thermal decomposition of petroleum naphtha and vinyl toluene, and hydrides obtained by copolymerizing these.

The softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and even more preferably 70 to 150 ° C.
In the present specification, the "softening point" of the tackifier means a value measured in accordance with JIS K 2531.
The tackifier may be used alone, or two or more kinds having different softening points, structures, etc. may be used in combination.
When two or more kinds of tackifiers are used, it is preferable that the weighted average of the softening points of the plurality of tackifiers belongs to the above range.

The content of the tackifier is preferably 0.01 to 65 with respect 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 by mass, more preferably 0.1 to 50% by mass, still more preferably 1 to 40% by mass, and even more preferably 2 to 30% by mass.

(Additives for adhesives)
In one aspect of the present invention, the pressure-sensitive adhesive composition (x) contains an additive for a pressure-sensitive adhesive used in a general pressure-sensitive adhesive in addition to the above-mentioned additives as long as the effect of the present invention is not impaired. You may be doing it.
Examples of such additives for adhesives include antioxidants, softeners (plasticizers), rust preventives, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents and the like. Can be mentioned.
These adhesive additives may be used alone or in combination of two or more.
When these adhesive additives are contained, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 with respect to 100 parts by mass of the adhesive resin. It is 10 parts by mass.

When the support layer (II) of the second aspect described above having the first pressure-sensitive adhesive layer (X1) which is the expandable pressure-sensitive adhesive layer is used, the first pressure-sensitive adhesive layer (X1) which is the expandable pressure-sensitive adhesive layer The forming material is formed from the expansive pressure-sensitive adhesive composition (x11) further containing the heat-expandable particles in the above-mentioned pressure-sensitive adhesive composition (x).
The heat-expandable particles are as described above.
The content of the heat-expandable particles is preferably 1 to 1 with respect to the total amount (100% by mass) of the active ingredient of the expandable pressure-sensitive adhesive composition (x11) or the total amount (100% by mass) of the expandable pressure-sensitive adhesive layer. It is 70% by mass, more preferably 2 to 60% by mass, still more preferably 3 to 50% by mass, and even 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, the pressure-sensitive adhesive composition (x), which is a material for forming the non-expandable pressure-sensitive adhesive layer, preferably does not contain heat-expandable particles.
When the heat-expandable particles are contained, the content thereof is preferably as small as possible, and 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). On the other hand, it is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.

As in the laminates 2a and 2b shown in FIG. 2, a support layer (II) having a first pressure-sensitive adhesive layer (X1) and a second pressure-sensitive adhesive layer (X2), which are non-expandable pressure-sensitive adhesive layers, is used. If, at 23 ° C., the storage shear modulus G of the first pressure-sensitive adhesive layer is a non-expandable pressure-sensitive adhesive layer (X1) '(23) is preferably not more than 1.0 × ¹⁰ 8 Pa, more preferably 5. It is 0 × 10 ⁷ Pa or less, more preferably 1.0 × 10 ⁷ Pa or less.
If intumescent storage shear modulus G '(23) of the first pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer (X1) is less than 1.0 × ¹⁰ 8 Pa, for example, laminate 2a shown in FIG. 2, 2b The first pressure-sensitive adhesive layer (X1) is in contact with the cured resin layer (I') due to the expansion of the heat-expandable particles in the expandable base material layer (Y1) due to the heat expansion treatment. ) Is likely to form irregularities on the surface.
As a result, a laminate that can be easily separated at the interface P between the support layer (II) and the cured resin layer (I') with a slight force can be obtained.
The storage shear elastic modulus G'(23) of the first pressure-sensitive adhesive layer (X1), which is a non-expandable pressure-sensitive adhesive layer, at 23 ° C. is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5. It is 0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

The light transmittance of the support layer (II) of the laminate of one aspect of the present invention at a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, still more preferably 70% or more. When the light transmittance is in the above range, the energy ray-curable resin layer (I) is cured when the energy ray-curable resin layer (I) is irradiated with energy rays (ultraviolet rays) via the support layer (II). The degree is improved. The upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, but can be, for example, 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) contained in the support layer (II) contain a colorant, the effects of the present invention are not impaired. It is preferable to adjust its content.
When a colorant is contained, the content thereof is preferably as small as possible, with respect 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 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, and in the substrate (Y). The content of the colorant is preferably less than 1% by mass, more preferably less than 1% by mass, based on the total amount (100% by mass) of the active ingredient of the resin composition (y) or the total amount (100% by mass) of the base material (Y). It is less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably less than 0.001% by 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 irradiating energy rays. For example, from an energy ray-curable resin composition containing an energy ray-curable component (a). It is what is formed.

[Energy ray curable component (a)]
The energy ray-curable component (a) is a component that is cured by irradiation with energy rays.
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 80,000 to 2000000 (hereinafter, also simply referred to as “polymer (a1)”). , Compound (a2) having an energy ray-curable double bond and having a molecular weight of 100 to 80,000 (hereinafter, also simply referred to as “compound (a2)”) and the like can be mentioned.
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 80,000 to 2000,000.
Examples of the polymer (a1) include an acrylic polymer (a11) having a functional group X capable of reacting with a group of another compound, a group Y reacting with the functional group X, and an energy ray-curable double. Examples thereof include an acrylic resin (a1-1) obtained by polymerizing an energy ray-curable compound (a12) having a bond with the energy ray-curable compound (a12).
The polymer (a1) may be used alone or in combination of two or more.

-Acrylic polymer (a11)
Examples of the functional group X contained in the acrylic polymer (a11) include a hydroxyl group, a carboxy group, an amino group, and a substituted amino group (one or two hydrogen atoms of the amino group are substituted with a group other than the hydrogen atom. One or more selected from the group consisting of a group consisting of an epoxy group and an epoxy group.

Examples of the acrylic polymer (a11) include those obtained by copolymerizing an acrylic monomer having the functional group X and an acrylic monomer having no functional group X, and other than these monomers. Further, a monomer other than the acrylic monomer (non-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) acrylic. Hydroxyalkyl (meth) acrylates such as 2-hydroxybutyl acid, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; non- (meth) acrylic unsaturateds such as vinyl alcohols and allyl alcohols. Alcohol (unsaturated alcohol having no (meth) acrylic skeleton) and the like can be mentioned.
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; fumaric acid, itaconic acid, maleic acid, and citraconic acid. Such as ethylenically unsaturated dicarboxylic acid (dicarboxylic acid having an ethylenically unsaturated bond); anhydride of the above ethylenically unsaturated dicarboxylic acid; (meth) acrylic acid carboxyalkyl ester such as 2-carboxyethyl methacrylate. ..
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) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth) acrylic acid. n-butyl, 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, (meth) ) Undecyl acrylate, dodecyl (meth) acrylate (lauryl acrylate (meth), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, ( The alkyl groups that make up the alkyl ester, such as hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), have a carbon number of carbon atoms. Examples thereof include (meth) acrylic acid alkyl esters having a chain structure of 1 to 18.
Examples of the acrylic monomer having no functional group X include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. Acrylic acid group-containing (meth) acrylic acid ester; (meth) acrylic acid ester having an aromatic group, including (meth) acrylic acid aryl ester such as phenyl (meth) acrylic acid; non-crosslinkable (meth) Acrylamide and derivatives thereof; (meth) acrylic acid esters having non-crosslinkable tertiary amino groups such as (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, etc. Can be mentioned.
Examples of the non-acrylic monomer include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

In the acrylic polymer (a11), the content of the amount of the structural unit derived from the acrylic monomer having the functional group X is preferably 0.1 to 50% by mass, based on the total amount of the structural units constituting the polymer (a11). It is 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.
Examples of the group Y include one or more selected from the group consisting of an isocyanate group, an epoxy group and a carboxy group, 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 contained 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 reacting a diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth) acrylate; Obtained by reacting a diisocyanate compound or polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate. Examples thereof include acryloyl monoisocyanate compounds. Of these, 2-methacryloyloxyethyl isocyanate is preferable.

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

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

The mass average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 20,000, more preferably 300,000 to 1,500,000.

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

(Compound (a2))
Compound (a2) is a compound having an energy ray-curable double bond and having a molecular weight of 100 to 80,000.
As the energy ray-curable double bond of the compound (a2), a (meth) acryloyl group, a vinyl group and the like 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, a phenol resin having an energy ray-curable double bond, and the like. ..
Compound (a2) may be used alone or in combination of two or more.

Examples of the low molecular weight compound having an energy ray-curable double bond include polyfunctional monomers and oligomers, and acrylate compounds having a (meth) acryloyl group are 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, and 2,2-bis [4-. ((Meta) acryloxipolyethoxy) phenyl] propane, ethoxylated bisphenol A di (meth) acrylate, 2,2-bis [4-((meth) acryloxidiethoxy) phenyl] propane, 9,9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 2,2-bis [4-((meth) acryloyloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol di (meth) acrylate (tricyclo) Decandymethylol di (meth) acrylate), 1,10-decanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dipropylene glycol di (Meta) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene 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 and other bifunctional (meth) acrylates; tris (2- (meth) acryloxyethyl) isocyanurate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocia Nurate, glycerin tri (meth) acrylate ethoxylated, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate ethoxylated, pentaerythritol tetra Polyfunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate; urethane (meth) acrylate Examples thereof include polyfunctional (meth) acrylate oligomers such as ligomer.

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

The mass average molecular weight (Mw) of compound (a2) is preferably 100 to 30,000, more preferably 300 to 10,000.

The content of the compound (a2) is preferably 1 with respect to the total amount (100% by mass) of the active ingredient of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). It is ~ 40% by mass, more preferably 2 to 30% by mass, still more preferably 3 to 20% by mass.

[Polymer without energy ray-curable double bond (b)]
When the energy ray-curable resin composition contains the compound (a2), the energy ray-curable resin composition further contains a polymer (b) having no energy ray-curable double bond (hereinafter, also simply referred to as “polymer (b)”). It is preferable to do so.
The polymer (b) may be used alone or in combination of two or more.

Examples of the polymer (b) include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, acrylic urethane resins, polyvinyl alcohol (PVA), butyral resins, polyester urethane resins and the like. 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 kind of acrylic monomer or a copolymer of two or more kinds of acrylic monomers. It may be a copolymer of one kind or two or more kinds of acrylic monomers and a monomer other than one kind or two or more kinds of acrylic monomers (non-acrylic monomers).

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

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n-butyl (meth) acrylic acid. , (Meta) isobutyl acrylate, (meth) sec-butyl acrylate, (meth) tert-butyl acrylate, (meth) pentyl acrylate, (meth) hexyl acrylate, (meth) heptyl acrylate, (meth) 2-Ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate Undecyl, dodecyl (meth) acrylate (lauryl acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl acrylate), pentadecyl (meth) acrylate, (meth) acrylic The alkyl groups constituting the alkyl ester, such as hexadecyl acid (palmicyl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate), have 1 to 18 carbon atoms. Examples thereof include (meth) acrylic acid alkyl ester having a chain structure of.

Examples of the (meth) acrylic acid ester having a cyclic skeleton include (meth) acrylic acid cycloalkyl ester such as (meth) acrylic acid isobornyl and (meth) acrylic acid dicyclopentanyl; and (meth) acrylic acid benzyl and the like. (Meta) Acrylic acid aralkyl ester; (Meta) Acrylic acid cycloalkenyl ester such as (meth) Acrylic acid dicyclopentenyl ester; (Meta) Acrylic acid cycloalkenyloxyalkyl such as (meth) Acrylic acid dicyclopentenyloxyethyl ester Esters and the like can be mentioned.

Examples of the glycidyl group-containing (meth) acrylic acid ester include glycidyl (meth) acrylic acid.
Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. , 2-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.
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 and the like.

The polymer (b) may be at least partially crosslinked by the crosslinking agent (e) or may not be crosslinked.
Examples of the polymer (b) in which at least a part thereof is crosslinked by the cross-linking agent (e) include those in which the reactive functional group in the polymer (b) has reacted with the cross-linking agent (e).
The reactive functional group may be appropriately selected depending on the type of the cross-linking agent (e) and the like, and is not particularly limited. For example, when the cross-linking agent (e) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxy group, an amino group and the like, and among these, the reactivity with the isocyanate group is high. High hydroxyl groups are preferred. When the cross-linking 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, the reactivity with the epoxy group. A carboxy group having a high value is preferable. However, in terms of preventing corrosion of the circuits of the semiconductor wafer and the semiconductor chip, the reactive functional group is preferably a group other than the carboxy group.

Examples of the polymer (b) having the above-mentioned reactive functional group include those obtained by polymerizing at least the monomer having the above-mentioned reactive functional group. In the case of the acrylic polymer (b-1), one or both of the above-mentioned acrylic-based monomer and non-acrylic-based monomer mentioned as the monomers constituting the acrylic polymer (b-1) has the above-mentioned reactive functional group. It may be used. For example, as the polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylic acid ester can be mentioned, and in addition to this, the above-mentioned polymer (b) mentioned above can be mentioned. Examples thereof include acrylic monomers and non-acrylic monomers obtained by polymerizing a monomer in which one or more hydrogen atoms are substituted with the above reactive functional groups.

In the polymer (b), the content of the structural unit derived from the monomer having a reactive functional group is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, based on the total amount of the structural units constituting the polymer (b). be. When the content of the structural unit is in the above range, the degree of cross-linking in the polymer (b) is in a more preferable range.

The mass average molecular weight (Mw) of the polymer (b) is preferably 1000 to 2000000, more preferably 100,000 to 1500,000 from the viewpoint of improving the film-forming property of the energy ray-curable resin composition.

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

The total content of the energy ray-curable component (a) and the polymer (b) is the total amount (100% by mass) of the active component of the energy ray-curable resin composition or the total amount of the energy ray-curable resin layer (I) ( It is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and further preferably 15 to 70% by mass with respect to 100% by mass). When the total content is in 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 the energy ray-curable. The amount is preferably 3 to 160 parts by mass, and more preferably 6 to 130 parts by mass with respect to 100 parts by mass of the sex component (a). When the content of the polymer (b) is in the above range, the energy ray curability becomes better.

In addition to the energy ray-curable component (a) and the polymer (b), the energy ray-curable resin composition contains a photopolymerization initiator (c), a coupling agent (d), and a cross-linking agent (e), depending on the purpose. ), Coloring agent (g), thermosetting component (f), curing accelerator (g), filler (h) and general-purpose additive (z). May be good. For example, the energy ray-curable resin layer (I) formed by using the energy ray-curable resin composition containing the energy ray-curable component (a) and the thermosetting component (f) is covered by heating. The adhesive force to the body is improved, and the strength of the cured resin layer (I') formed from the energy ray-curable resin layer (I) is also improved.

[Photopolymerization Initiator (c)]
Examples of the photopolymerization initiator (c) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate and benzoin dimethyl ketal; acetophenone, 2 Acetphenone compounds such as −hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxide compounds such as phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthium monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenylketone Azo compounds such as azobisisobutyronitrile; Titanocene compounds such as titanosen; thioxanthone compounds such as thioxanthone; benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, Benzophenone compounds such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-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-chloroanthraquinone and the like. Further, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine can also be used.
The photopolymerization initiator (c) may be used alone or in combination of two or more.
The content of the photopolymerization initiator (c) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is preferably 0. It is 01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and further preferably 0.05 to 5 parts by mass.

[Coupling agent (d)]
By using a coupling agent (d) having a functional group capable of reacting with an inorganic compound or an organic compound, the adhesion of the energy ray-curable resin layer (I) can be improved, and the energy rays can be improved. The cured resin layer (I') formed by curing the curable resin layer (I) improves water resistance without impairing heat resistance.
The coupling agent (d) may be used alone or in combination of two or more.

The coupling agent (d) is preferably a compound having a functional group capable of reacting with the functional groups of the energy ray-curable component (a), the polymer (b) and the like, and is preferably a silane coupling agent. More preferred.
Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, and 2- (3). , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) ) Ppropylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane , Bis (3-triethoxysilylpropyl) tetrasulfan, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like.

The content of the coupling agent (d) in the energy ray-curable resin composition or the energy ray-curable resin layer (I) is 100 parts by mass in total of the energy ray-curable component (a) and the polymer (b). On the other hand, it is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass. When the content of the coupling agent (d) is equal to or higher than the above lower limit, the effects of improving the dispersibility of the filler in the resin and improving the adhesiveness of the energy ray-curable resin layer (I) are more remarkable. Therefore, when it is equal to or less than the above upper limit value, the generation of outgas is suppressed.

[Crosslinking agent (e)]
By cross-linking the energy ray-curable component (a), the polymer (b) and the like with the cross-linking agent (e), the initial adhesive force and the cohesive force of the energy ray-curable resin layer (I) can be adjusted.
The cross-linking agent (e) may be used alone or in combination of two or more.

Examples of the cross-linking agent (e) include an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based cross-linking agent (a cross-linking agent having a metal chelate structure), an aziridine-based cross-linking agent (a cross-linking agent having an aziridinyl group), and the like. Can be mentioned.

Examples of the organic polyvalent isocyanate compound include an aromatic polyvalent isocyanate compound, an aliphatic polyhydric isocyanate compound, and an alicyclic polyvalent isocyanate compound (hereinafter, these compounds are collectively abbreviated as "aromatic polyvalent isocyanate compound and the like". ); Trimerics such as the above aromatic polyhydric isocyanate compounds, isocyanurates and adducts; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds with polyol compounds, etc. Can be mentioned.
The above-mentioned "adduct" includes the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyhydric isocyanate compound or alicyclic polyvalent isocyanate compound, and low levels of ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like. It means a reaction product with a molecularly active hydrogen-containing compound, and examples thereof include a xylylene diisocyanate adduct of trimethylol propane as described later. Further, the "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the terminal portion of the molecule.

More specifically, as the organic polyvalent 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; trimethylolpropane Compounds in which any one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or some hydroxylates of the polyols such as lysine diisocyanate.

Examples of the organic polyvalent imine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinyl propionate, and tetramethylolmethane-. Examples thereof include tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

When an organic polyvalent isocyanate compound is used as the cross-linking agent (e), it is preferable to use a hydroxyl group-containing polymer as the energy ray-curable component (a) and / or the polymer (b). When the cross-linking agent (e) has an isocyanate group and the energy ray-curable component (a) and / or the polymer (b) has a hydroxyl group, the cross-linking agent (e) and the energy ray-curable component (a) and / Alternatively, the crosslinked structure can be easily introduced into the energy ray-curable resin layer (I) by the reaction with the polymer (b).

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

[Thermosetting component (f)]
Examples of the thermosetting component (f) include epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, and silicone resins. Among these, epoxy-based thermosetting resins are preferable.
The thermosetting component (f) may be used alone or in combination of two or more.

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

Examples of the epoxy resin (f1) include known ones, such as polyfunctional epoxy resin, bisphenol A diglycidyl ether and its hydrogenated product, orthocresol novolac epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy. Examples thereof include bifunctional or higher functional epoxy compounds such as resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins.
The epoxy resin (f1) may be used alone or in combination of two or more.

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

The number average molecular weight of the epoxy resin (f1) is preferably 300 to 30,000, more preferably 300,000 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'). It is 400 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 thermosetting agent (f2) functions as a curing agent for the epoxy resin (f1).
Examples of the thermosetting 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, a group in which an acid group is annealed, and the like, and the phenolic hydroxyl group, an amino group, or an acid group is annealed. It is preferably a group, more preferably a phenolic hydroxyl group or an amino group.
The thermosetting agent (f2) may be used alone or in combination of two or more.

Among the heat-curing agents (f2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins.
Among the thermosetting agents (f2), examples of the amine-based curing agent having an amino group include dicyandiamide and the like.
The content of the thermosetting agent (f2) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin (f1).

The content of the thermosetting component (f) (for example, the total content of the epoxy resin (f1) and the thermosetting agent (f2)) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b). It is a department.

[Curing accelerator (g)]
The curing accelerator (g) is a component for adjusting the curing rate of the energy ray-curable resin layer (I).
Preferred curing accelerators (g) include, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole. , 2-Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and other imidazoles; tributylphosphine, diphenylphosphine, triphenylphosphine and the like. Organic phosphins; tetraphenylphosphonium tetraphenylborate, tetraphenylborone salts such as triphenylphosphine tetraphenylborate and the like can be mentioned.
When the curing accelerator (g) is used, the content of the curing accelerator (g) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermosetting component (f).

[General-purpose additive (z)]
The general-purpose additive (z) may be a known one, and may be arbitrarily selected depending on the intended purpose, and is not particularly limited. For example, a filler, a colorant, a plasticizer, an antistatic agent, an antioxidant, and a gettering agent. And so on.
The general-purpose additive (z) may be used alone or in combination of two or more.

Examples of the filler include an inorganic filler and an organic filler, and by using these, the coefficient of thermal expansion of the cured resin layer (I') can be adjusted.
The energy ray-curable resin layer (I) may or may not contain a filler, but when the filler is contained, the content thereof makes the occurrence of warpage more effective. From the viewpoint of suppression, preferably 5 to 87% by mass with respect to the total amount (100% by mass) of the active ingredient of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , More preferably 7 to 78% by mass.
Examples of the filler include those made of a heat conductive material.
Examples of the inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like; spherical beads of these inorganic fillers; surface-modified products of these inorganic fillers. Monocrystalline fibers of these inorganic fillers; glass fibers and the like.
The average particle size of the filler is preferably 0.01 to 20 μm, more preferably 0.1 to 15 μm, and even more preferably 0.3 to 10 μm. When the average particle size of the filler is in the above range, it is possible to suppress a decrease in the transmittance of the energy ray-curable resin layer (I) 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, specifically. , Preferably less than 5% by mass, more preferably 0, based on the total amount (100% by mass) of the active ingredient of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). .. Less than 1% by mass, more preferably less than 0.01% by mass, even more preferably less than 0.001% by mass.

<< Manufacturing method of energy ray curable resin composition >>
The energy ray-curable resin composition can be obtained by blending each component for constituting the energy ray-curable resin composition.
The order of addition of each component at the time of blending is not particularly limited, and two or more kinds of components may be added at the same time.
When a solvent is used, it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or diluting any of the compounding components other than the solvent in advance. You may use it by mixing the solvent with these compounding components without leaving.
The method of mixing each component at the time of blending is not particularly limited, and from known methods such as a method of rotating a stirrer or a stirring blade to mix; a method of mixing using a mixer; a method of adding ultrasonic waves to mix. It may be selected as appropriate.
The temperature and time at the time of adding and mixing 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; acetone. , Ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds having an amide bond) and the like. Among these, methyl ethyl ketone, toluene, and ethyl acetate are preferable from the viewpoint that the components contained in the energy ray-curable resin composition can be mixed more uniformly. The solvent may be used alone or in combination of two or more.

The energy ray-curable resin layer (I) may have a single-layer structure or may be composed of a plurality of layers of two or more layers.
The energy ray-curable resin layer (I) composed of two or more layers includes, for example, an energy ray-curable resin layer (I-) for imparting a cured resin layer (I') having a high storage elastic modulus E'. Examples thereof include those having i) and an energy ray-curable resin layer (I-ii) having a high adhesive strength. When having such a configuration, by arranging the energy ray-curable resin layer (I-ii) on the surface on the side on which the object to be sealed is placed, the object to be sealed can be firmly fixed. After curing, the cured resin layer (I') formed by curing the energy ray-curable resin layer (I-i) effectively suppresses warpage, so that it has performance as a temporary fixing layer and a warp prevention layer. It is possible to achieve a higher level of compatibility with the above performance. The preferable compositions and physical properties of the energy ray-curable resin layers (I-i) and (I-ii) corresponded to the desired functions from the preferable compositions and physical properties of the energy ray-curable resin layer (I) described above. It may be selected and applied as appropriate.

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, still more preferably 15 to 100 μm, still more preferably 20 to 50 μm. be. When the thickness of the energy ray-curable resin layer (I) is at least the above lower limit value, a cured encapsulant whose warpage is more effectively suppressed can be obtained, and when it is at least the above upper limit value, the cost is increased. Can be suppressed and excellent curability can be obtained.
Here, the "thickness of the energy ray-curable resin layer (I)" means the thickness of the entire energy ray-curable resin layer (I), and for example, the energy ray-curable resin layer composed of two or more layers. The thickness of (I) means the total thickness of all the layers constituting the energy ray-curable resin layer (I).

The storage elastic modulus E'of the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) at 23 ° C. suppresses warpage and has a cured seal with a cured resin layer having a flat surface. From the viewpoint of making the stop body a manufacturable laminate, 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, and further. It is preferably 1.0 × 10 ⁹ or more, 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, and more. More preferably, it is 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, still more preferably 30% or more, still more preferably 50% or more. Is. When the visible light transmittance is in the above range, sufficient energy ray curability can be obtained. The upper limit of the visible light transmittance is not limited, but can 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 aspect 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 so as to have a desired configuration. It can be manufactured by laminating. Each layer can be formed, for example, by applying and drying a resin composition for forming each layer on a release material.
However, the method for producing a laminate according to one aspect of the present invention is not limited to the above method, and for example, the base material (Y) is placed on the pressure-sensitive adhesive layer (X) formed on the release material. As in the method of applying the resin composition (y) for forming and further applying the energy ray-curable resin composition on the resin composition (y), the resin composition is sequentially applied onto a specific layer to form a layer. It may be a method of forming and forming multiple layers. At that time, a plurality of layers may be applied at the same time using, for example, a multi-layer coater.

[Manufacturing method of cured sealant]
The method for producing a cured encapsulant according to one aspect of the present invention is a method for producing a cured encapsulant using the laminate according to one aspect of the present invention, and has the following steps (i) to (iv).
Step (i): Place the object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate Step (ii): On the energy ray-curable resin layer (I) Step of irradiating energy rays to form a cured resin layer (I') formed by curing the energy ray-curable resin layer (I) Step (iii): The encapsulation object and the encapsulation object At least the surface of the cured resin layer (I') in the peripheral portion is coated with a thermosetting encapsulant, and the encapsulant is thermosetting to form a cured encapsulant containing the encapsulating object. Step Step (iv): By the treatment of expanding the thermosetting particles, the cured resin layer (I') and the support layer (II) are separated at the interface thereof to obtain a cured sealing body with a cured resin layer. Step The cured encapsulant in one aspect of the present invention is formed by coating an object to be sealed with a sealing material and curing the encapsulant, and is a material of the object to be sealed and the encapsulant. It is composed of a cured product.

FIG. 4 is a schematic cross-sectional view showing a process of manufacturing a cured sealed body using the laminated body 1a shown in FIG. 1 (a). Hereinafter, each step described above will be described with reference to FIG. 4 as appropriate.

<Step (i)>
The step (i) is a step of placing the object to be sealed on a part of the surface of the energy ray-curable resin layer (I) contained in the laminate of one aspect of the present invention.
In FIG. 4A, the adhesive surface of the adhesive layer (X) of the support layer (II) is attached to the support 50 by using the laminate 1a in this step, and the energy ray curable resin layer ( A state in which the object to be sealed 60 is placed on a part of the surface of I) is shown.
Note that FIG. 4A shows an example in which the laminate 1a shown in FIG. 1A is used, but the same applies when the laminate of one aspect of the present invention having another configuration is used. The support, the laminated body, and the object to be sealed are laminated or placed in this order.

The temperature condition in the step (i) is preferably a temperature at which the thermally expandable particles do not expand, for example, in an environment of 0 to 80 ° C. (however, the expansion start temperature (t) is 60 to 80 ° C.). In this case, it is preferable to carry out the operation in an environment of less than the expansion start temperature (t).

The support is preferably attached to the entire surface of the adhesive surface of the adhesive layer (X) of the laminated body.
Therefore, the support is preferably plate-shaped. Further, as shown in FIG. 4, the area of the adhesive surface of the pressure-sensitive adhesive layer (X) and the surface of the support on the side to be attached is preferably equal to or larger than the area of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer (X).

As the material constituting the support, it is appropriate to consider the required characteristics such as mechanical strength and heat resistance according to the type of the object to be sealed, the type of the sealing material used in the step (ii), and the like. Be selected.
Specific materials constituting the support include metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, and polyimide resins. Resin materials such as polyamideimide resin; composite materials such as glass epoxy resin are mentioned, and among these, SUS, glass, silicon wafer and the like are preferable. Further, from the viewpoint of enabling the energy ray-curable resin layer (I) to be irradiated with energy rays via the support, the support is preferably a transparent material such as glass.
Examples of engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like.
Examples of super engineering plastics include polyphenylene sulfide (PPS), polyethersulfone (PES), and polyetheretherketone (PEEK).

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

On the other hand, examples of the object to be sealed placed on a part of the surface of the energy ray-curable resin layer (I) include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and the like. Examples include panel substrates.

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 an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface thereof.
The semiconductor chip is preferably placed so that the back surface opposite to the circuit surface is covered with the surface of the energy ray-curable resin layer (I). In this case, the circuit surface of the semiconductor chip is exposed after mounting.
A 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 form of the target package, the number of production, and the like.

Here, in the laminate of one aspect of the present invention, a region larger than the chip size is covered with a sealing material, such as FOWLP and FOPLP, and not only the circuit surface of the semiconductor chip but also the sealing material. It is preferable that it is applied to a package that forms a rewiring layer even in the surface region of the above.
Therefore, the semiconductor chip is placed on a part of the surface of the energy ray-curable resin layer (I), and a plurality of semiconductor chips are aligned on the surface at regular intervals. It is preferable that the semiconductor chips are mounted, and it is more preferable that the plurality of semiconductor chips are mounted on the surface in a state of being arranged 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 according to the form of the target package and 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). be.
FIG. 4B shows a state in which the energy ray-curable resin layer (I) is cured in this step to form the cured resin layer (I').
The type and irradiation condition of the energy ray are not particularly limited as long as the type and condition are such that the energy ray-curable resin layer (I) is cured to the extent that the energy ray-curable resin layer (I) sufficiently exerts its function. It may be appropriately selected according to the process to be performed.
During curing of the energy ray-curable resin layer (I), the illuminance of the energy ray is preferably 4~280mW / cm ^2, wherein at the time of curing, the amount of energy rays, 5~1000mJ / cm ² is Preferably, 100 to 500 mJ / cm ² is more preferable.
The types of energy rays and the irradiation device are as described above.
The energy rays may be irradiated from any direction as long as the energy rays can be irradiated to the energy ray-curable resin layer (I). For example, the support (II) and the support 50 have a light transmittance. By using an excellent material, the energy is incident through the support (II) and the support 50 (that is, from the surface of the support 50 opposite to the pressure-sensitive adhesive layer (X) in FIG. 4 (b). The support 50 (passing through the pressure-sensitive adhesive layer (X) and the base material (Y)) and the energy ray-curable resin layer (I) can be irradiated with energy rays.

<Process (iii)>
In step (iii), the object to be sealed and the surface of the cured resin layer (I') at least in the peripheral portion of the object to be sealed are coated with a thermosetting sealing material (hereinafter, “coating treatment”). This is a step of thermally curing the encapsulant to form a cured encapsulant containing the encapsulant.
In the coating treatment, first, the object to be sealed and at least the peripheral portion of the surface of the cured resin layer (I') of the object to be sealed are coated with a sealing material.
The sealing material covers the entire exposed surface of the object to be sealed, and is also filled in the gaps between the plurality of semiconductor chips.
For example, FIG. 4C shows a state in which the sealing material 70 covers the entire surface of the sealing object 60 and the cured resin layer (I').

The sealing material has a function of protecting the object to be sealed and the elements associated therewith from the external environment.
The encapsulant used in the production method of one aspect of the present invention is a thermosetting encapsulant containing a thermosetting resin.
Further, the encapsulant may be a solid such as granules, pellets or a film at room temperature, or may be a liquid in the form of a composition, but from the viewpoint of workability, the encapsulant may be a film. A sealing resin film which is a sealing material of the above is preferable.

The coating method can be appropriately selected and applied according to the type of encapsulant from the methods applied in the conventional encapsulation step. For example, a roll laminating method, a vacuum pressing method, or a vacuum laminating method can be applied. A method, a spin coating method, a die coating method, a transfer molding method, a compression molding method, or 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 by the sealing material.
The heat curing treatment in step (iii) is performed at a temperature at which the heat-expandable particles do not expand. For example, when a laminate having a layer containing the heat-expandable particles is used, the heat-expandable particles start to expand. It is preferably carried out under temperature conditions lower than the temperature (t).

In the production method of one aspect of the present invention, as shown in FIG. 4C, a cured resin layer (I') is provided on the surface of the object to be sealed 60 sealed with the sealing material 70. In this state, heat curing treatment is performed.
Since the cured resin layer (I') is provided, the difference in shrinkage stress between the two surfaces of the obtained cured encapsulant can be reduced, and the warpage generated in the cured encapsulant can be effectively suppressed. Conceivable.

<Process (iv)>
In step (iv), the cured resin layer (I') and the support layer (II) are separated at the interface by the treatment of expanding the heat-expandable particles to obtain a cured sealant with a cured resin layer. It is a process.
FIG. 4D 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. 4D, with a cured resin layer having a cured sealing body 80 formed by sealing the sealing object 60 by separating at the interface P and a cured resin layer (I'). A cured sealant 100 can be obtained.
The presence of the cured resin layer (I') has a function of effectively suppressing the warp generated in the cured encapsulant, protects the object to be sealed, and improves the reliability of the object to be sealed. Contribute.

The "expansion process" in the step (iv) is a process of expanding the thermally expandable particles by heating the thermally expandable particles at an expansion start temperature (t) or higher, and the cured resin layer (I) is expanded by the process. The surface of the support layer (II) on the') side has irregularities. As a result, they can be easily separated at the interface P with a slight force.
The "temperature above the expansion start temperature (t)" when expanding the thermally expandable particles is preferably "expansion start temperature (t) + 10 ° C." or more and "expansion start temperature (t) + 60 ° C." or less. , "Expansion start temperature (t) + 15 ° C." or more, "Expansion start temperature (t) + 40 ° C." or less is more preferable.
The heating method is not particularly limited, and examples thereof include a heating method using a hot plate, an oven, a baking furnace, an infrared lamp, a hot air blower, or the like, and the support layer (II) and the cured resin layer (I') are used. From the viewpoint of facilitating separation at the interface P, a method in which the heat source for heating can be provided on the support 50 side is preferable.

The cured encapsulant with a cured resin layer thus obtained is further subjected to necessary processing. An example thereof will be described below. In the following description, an embodiment in which the semiconductor chip 60 is used as the sealing object 60 will be described.

<First grinding process>
FIG. 5 (a) shows the cured encapsulant 100 with a cured resin layer obtained by the above manufacturing method, and FIG. 5 (b) shows the cured resin layer (I') of the cured encapsulant 80. The first grinding step is shown in which the surface 100a on the opposite side is ground by the grinding means 110 to expose the circuit surface 60a of the semiconductor chip 60.
The grinding means 110 is not particularly limited, and a known grinding device such as a grinder may be used.
When carrying out the first grinding step, from the viewpoint of workability, it is preferable that the surface of the cured encapsulant on the cured resin layer (I') side is fixed on another support.
Further, from the viewpoint of workability, dicing may be performed in a predetermined size including one or a plurality of chips before the first grinding step.

<Rewiring layer and external terminal electrode forming process>
FIG. 5C shows a rewiring layer 200 and an external terminal electrode 300 that are electrically connected to the circuit surface 60a of the semiconductor chip 60 exposed on the surface of the cured sealing body 80 by the first grinding step. The wiring layer and external terminal electrode forming steps are shown.
The material of the rewiring 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, and alloys containing these metals. The rewiring 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 provided if necessary.
The external terminal electrode 300 is electrically connected to the external electrode pad of the rewiring layer 200. The external electronic electrode 300 can be formed by, for example, solder-bonding a solder ball or the like.

<Dicing process>
FIG. 5D shows a step of dicing the cured encapsulant 100 with a cured resin layer to which the external terminal electrode 300 is connected.
Dicing may be performed in units of one semiconductor chip, or dicing may be performed in a predetermined size including a plurality of semiconductor chips. The method for dicing the cured encapsulant 100 with a cured resin layer is not particularly limited, and can be carried out by a cutting means such as a dicing saw.

<Second grinding process>
FIG. 5E shows a second grinding step in which the cured resin layer (I') arranged on the side opposite to the rewiring layer 200 of the cured sealing body 80 is ground by the grinding means 110. ing. At this time, it is preferable that the surface of the cured sealing body 80 on the rewiring layer 200 side is fixed with a back grind tape or the like. As the grinding means 110, the same means as in the first grinding step can be mentioned.
In the second grinding step, a part of the cured resin layer (I') may be ground, or the entire cured resin layer (I') may be ground.
By grinding the cured resin layer (I'), the obtained semiconductor package can be further miniaturized. Therefore, from this point of view, it is preferable to grind the entire 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') also plays a role of protecting the back surface of the semiconductor chip 60. be able to.

The present embodiment will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.
In the following description, the curable resin layer (I) means both the “energy ray curable resin layer (I)” and the “thermosetting resin layer”.
The physical property values in each example are values measured by the following methods.

<Mass average molecular weight (Mw)>
It was measured under the following conditions using a gel permeation chromatograph device (manufactured by Tosoh Corporation, product name "HLC-8020"), and the value measured in terms of standard polystyrene was used.
(Measurement condition)
-Column: "TSK guard column HXL-L""TSK gel G2500HXL""TSK gel G2000HXL""TSK gel G1000HXL" (all manufactured by Tosoh Corporation) connected in sequence-Column temperature: 40 ° C
・ Developing solvent: tetrahydrofuran ・ Flow rate: 1.0 mL / min

<Measurement of thickness of each layer>
The measurement was performed using a constant pressure thickness measuring instrument manufactured by Teclock Co., Ltd. (model number: "PG-02J", standard: JIS K6783, Z 1702, Z 1709).

<Measurement method of expansion start temperature (t) and maximum expansion temperature of thermally expandable particles>
The expansion start temperature (t) of the thermally expandable particles used in each example was measured by the following method.
To an aluminum cup having a diameter of 6.0 mm (inner diameter: 5.65 mm) and a depth of 4.8 mm, 0.5 mg of heat-expandable particles to be measured is added, and an aluminum lid (diameter: 5.6 mm, thickness: 0. Prepare a sample on which 1 mm) is placed.
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 upper part of the aluminum lid by a pressurizer. Then, with a force of 0.01 N applied by the pressurizer, it is heated from 20 ° C. to 300 ° C. at a heating rate of 10 ° C./min, the amount of displacement of the pressurizer in the vertical direction is measured, and the displacement in the positive direction is measured. Let the displacement start temperature be the expansion start temperature (t).
The maximum expansion temperature was the temperature at which the displacement amount measured by the above method was maximized.

<Evaluation of warpage>
The curable resin layer (I) of the curable resin layer (I) forming sheet prepared in each example was attached 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 "Epofix Resin") and a curing agent (manufactured by Struers, product name "Epofix Hardener"). A product was prepared, and the resin composition was applied to the surface of the silicon wafer opposite to the curable resin layer (I) so as to have a thickness of 30 μm. As a result, a pre-curing measurement sample having a curable resin layer (I) / silicon wafer / thermosetting resin composition layer in this order was obtained.
Subsequently, when the curable resin layer (I) is an energy ray-curable resin layer (I), ultraviolet rays are emitted to an ultraviolet ray using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Co., Ltd.) with an illuminance of 215 mW / cm ^2. The energy ray-curable resin layer (I) was cured by irradiating it three times under the condition of a light amount of 187 mJ / cm ^{2, and a cured resin layer (I') was formed.} When the curable resin layer (I) was a thermosetting resin layer (I), it was heated at 180 ° C. for 60 minutes to be cured to form a cured resin layer (I'). Then, the thermosetting resin composition is heated and cured to form a thermosetting resin layer, and a post-curing measurement sample having a cured resin layer (I') / silicon wafer / thermosetting resin layer in this order is obtained. Obtained.
After the cured sample was placed on a horizontal table, it was visually observed and the presence or absence of warpage was evaluated based on the following criteria. Since the "silicon wafer / thermosetting resin layer" portion of the sample measured after curing has a configuration corresponding to a cured encapsulant formed by sealing a semiconductor chip with a thermosetting resin, the cured resin is evaluated in this evaluation. The performance of the layer (I') as a warp prevention layer can be evaluated.
A: The amount of warpage is 3 mm or less.
B: The amount of warpage is larger than 3 mm and less than 15 mm.
C: The amount of warpage is 15 mm or more.
When the silicon wafer / thermosetting resin layer was formed by the same procedure as above without attaching the curable resin layer (I), the amount of warpage was 15 mm.

<Evaluation of separability>
A silicon wafer is attached to the surface of the curable resin layer (I) of the laminates obtained in each example, and then the curable resin layer (I) is cured by energy rays or heat to cure the curable resin layer (I'). Was formed. Next, the cured resin layer (I') and the support layer (II) are separated by expanding the expandable base material layer (Y1) by a thermal expansion treatment, and the separability is evaluated based on the following criteria. bottom. The curing conditions of the curable resin layer (I) produced in each example and the thermal expansion treatment conditions of the support layer (II) were the same as those described in Examples 1 to 5 and Reference Example 1 described later. ..
A: It is separable, the appearance of the cured resin layer (I') is good, and there is no adhesive residue.
B: It is separable and the appearance of the cured resin layer (I') is good, but there is some adhesive residue.
C: It cannot be separated, there is adhesive 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 expansive substrate layer (Y1)>
The expansive substrate layer (Y1) having a thickness of 200 μm prepared for measuring the storage elastic modulus E'was set to a size of 5 mm in length × 30 mm in width × 200 μm in thickness, and the one from which the release material was removed was used as a test sample.
Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), the test start temperature is 0 ° C, the test end temperature is 300 ° C, the temperature rise rate is 3 ° C / min, the frequency is 1 Hz, and the amplitude is 20 μm. The storage elastic modulus E'of the test sample at a predetermined temperature was measured under the conditions 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 a circle with a diameter of 8 mm, and the release material was removed and superposed to obtain a thickness of 3 mm as a test sample. ..
A torsional shear method using a viscoelasticity measuring device (manufactured by Antonio Par, device name "MCR300") under the conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a heating rate of 3 ° C./min, and a frequency of 1 Hz. Measured the storage shear elastic modulus G'of the test sample at a predetermined temperature.

<Storage modulus E'of the cured resin layer (I')>
The test start temperature was obtained by using a cured resin layer (I) obtained in each example as a test piece and using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"). The storage elastic modulus E'of the formed cured resin layer (I') was measured at 23 ° C. under the conditions of 0 ° C., a test end temperature of 300 ° C., a heating rate of 3 ° C./min, a frequency of 11 Hz, and an amplitude of 20 μm. When the curable resin layer (I) is an energy ray-curable resin layer (I), the test piece uses an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Co., Ltd.) to illuminate 215 mW. / cm ^2, which was cured by irradiating three times under conditions of light intensity 187mJ / cm ^2, when the curable resin layer (I) is a thermosetting resin layer (I) is heated for 60 minutes at 180 ° C. It was made to be hardened.

Synthesis example 1
(Synthesis of "acrylic urethane resin" used for the expandable base material layer (Y1))
In a reaction vessel under a nitrogen atmosphere, the equivalent ratio of isophorone diisocyanate to 100 parts by mass of a polycarbonate diol (carbonate type diol) having a mass average molecular weight of 1,000 is 1 between the hydroxyl group of the polycarbonate diol and the isocyanate group of the isophorone diisocyanate. The mixture was blended so as to be 1/1, and 160 parts by mass of toluene was further added, and the mixture was reacted at 80 ° C. for 6 hours or more while stirring in a nitrogen atmosphere until the isocyanate group concentration reached the 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, and the mass was increased. A urethane prepolymer having an average molecular weight of 29000 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), 1- 1.1 parts by mass of thioglycerol and 50 parts by mass of toluene were added, and the temperature was raised to 105 ° C. with stirring. Then, in the reaction vessel, a solution obtained by further diluting 2.2 parts by mass of the radical initiator (manufactured by Japan Finechem Co., Ltd., product name "ABN-E") with 210 parts by mass of toluene was maintained at 105 ° C. for 4 hours. Dropped over.
After completion of the dropping, the reaction was carried out at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin having a mass average molecular weight of 105,000.

[Preparation of support layer (II) forming sheet]
Manufacturing example 1
(Support layer (II-A))
A support layer (II-A) forming sheet was prepared according to the following procedures (1-1) to (1-4).
Details of the materials used to form each layer are as follows.

<Adhesive resin>
Acrylic copolymer (i): It has a structural unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0 / 20.0 (mass ratio). Acrylic copolymer of Mw 600,000.
-Acrylic copolymer (ii): n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid = 86.0 / 8.0 / 5.0 / 1. An acrylic copolymer of Mw 600,000 having a structural unit derived from a raw material monomer consisting of 0 (mass ratio).
<Additives>
-Isocyanate cross-linking agent (i): manufactured by Tosoh Corporation, product name "Coronate L", solid content concentration: 75% by mass.
<Thermal expandable particles>
-Thermal expandable particles A: manufactured by Kureha Corporation, product name "S2640", expansion start temperature (t) = 208 ° C., average particle size (D ₅₀ ) = 24 μm, 90% particle size (D ₉₀ ) = 49 μm.
<Release material>
-Heavy release film: manufactured by Lintec Corporation, product name "SP-PET382150", polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone-based release agent on one side, thickness: 38 μm.
-Light release film: manufactured by Lintec Corporation, product name "SP-PET381031", PET film provided with a release agent layer formed from a silicone-based release agent on one side, thickness: 38 μm.

(1-1) Formation of First Adhesive Layer (X1) 5.0 parts by mass of the isocyanate-based cross-linking agent (i) is added to 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin. The parts were mixed, diluted with toluene, and stirred uniformly to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass.
Then, the pressure-sensitive adhesive composition is applied to the surface of the release agent layer of the heavy-release film (hereinafter, also referred to as “peeling-treated surface”) to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds. Then, a first pressure-sensitive adhesive layer (X1), which is a non-thermally expandable pressure-sensitive adhesive layer having a thickness of 5 μm, was formed.
Incidentally, at 23 ° C., the storage shear modulus G of the first pressure-sensitive adhesive layer (X1) '(23) was 2.5 × ¹⁰ 5 Pa.
The adhesive strength of the first pressure-sensitive adhesive layer (X1) at 23 ° C. measured based on the above method was 0.3 N / 25 mm.

(1-2) Formation of Second Adhesive Layer (X2) To 100 parts by mass of the solid content of the acrylic copolymer (ii), which is an adhesive resin, 0.8 mass of the isocyanate-based cross-linking agent (i) The parts were mixed, diluted with toluene, and stirred uniformly to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass.
Then, the pressure-sensitive adhesive composition is applied to the peel-treated surface of the light-release film to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds to obtain a second pressure-sensitive adhesive layer having a thickness of 10 μm. X2) was formed.
The storage shear elastic modulus G'(23) of the second pressure-sensitive adhesive layer (X2) at 23 ° C. was 9.0 × 10 ⁴ Pa.
The adhesive strength of the second pressure-sensitive adhesive layer (X2) at 23 ° C. measured based on the above method was 1.0 N / 25 mm.

(1-3) Preparation of Base Material (Y) To 100 parts by mass of the solid content of the acrylic urethane resin obtained in Synthesis Example 1, 6.3 parts by mass of the isocyanate-based cross-linking agent (i) was added, and dioctyl tinbis as a catalyst. A resin composition of 1.4 parts by mass of (2-ethylhexanoate) and the above-mentioned heat-expandable particles A, diluted with toluene, and uniformly stirred to have a solid content concentration (active ingredient concentration) of 30% by mass. The thing was prepared.
The content of the heat-expandable particles A was 20% by mass with respect to the total amount (100% by mass) of the active ingredient in the obtained resin composition.
Then, the resin composition is formed on the surface of a polyethylene terephthalate (PET) film having a thickness of 50 μm (manufactured by Toyobo Co., Ltd., product name “Cosmo Shine A4100”, probe tack value: 0 mN / 5 mmφ), which is a non-expandable base material. An object was applied to form a coating film, and the coating film was dried at 100 ° C. for 120 seconds to form an expandable base material layer (Y1) having a thickness of 50 μm.
Here, the PET film which is the non-expandable base material corresponds to the non-expandable base material layer (Y2).
As described above, a base material (Y) composed of an expandable base material layer (Y1) having a thickness of 50 μm and a non-expandable base material layer (Y2) having a thickness of 50 μm was prepared.

As a sample for measuring the storage elastic modulus E'and the probe tack value of the expandable base material layer (Y1), the resin composition was applied to the peeled surface of the light release film to form a coating film. The coating film was dried at an atmospheric temperature of 100 ° C. for 120 seconds to form an expandable base material layer (Y1) having a thickness of 200 μm in the same manner.
Then, based on the above-mentioned measuring method, the storage elastic modulus and the probe tack value at each temperature of the expandable base material layer (Y1) were measured. The measurement results were as follows.
-Storage modulus at 23 ° C. E'(23) = 2.0 × 10 ⁸ Pa
Storage elastic 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 = 0mN / 5mmφ

(1-4) Lamination of Each Layer The non-expandable base material layer (Y2) of the base material (Y) prepared in the above (1-3) and the second pressure-sensitive adhesive layer (X2) formed in the above (1-2). ), And the expandable base material layer (Y1) and the first pressure-sensitive adhesive layer (X1) formed in (1-1) above were bonded together.
Then, the light release film / second pressure-sensitive adhesive layer (X2) / non-expandable base material layer (Y2) / expandable base material layer (Y1) / first pressure-sensitive adhesive layer (X1) / heavy release film are applied in this order. A laminated support layer (II-A) forming sheet was produced.

Manufacturing example 2
(Support layer (II-B))
In Production Example 1, the heat-expandable particles A were changed to the following heat-expandable particles B, and the drying conditions after applying the resin composition to form a coating film were changed to 1 minute at an atmospheric temperature of 100 ° C. A sheet for forming a support layer (II-B) was produced in the same manner as in Production Example 1 except for the above.
-Thermal expandable particles B: manufactured by Nippon Phillite Co., Ltd., product name "031-40 DU", expansion start temperature (t) = 80 ° C.

Manufacturing example 3
(Support layer (II-C))
In Production Example 1, the heat-expandable particles A were changed to the following heat-expandable particles C, and the drying conditions after applying the resin composition to form a coating film were changed to 1 minute at an atmospheric temperature of 100 ° C. A sheet for forming a support layer (II-C) was produced in the same manner as in Production Example 1 except for the above.
-Thermal expandable particles C: manufactured by Nippon Phillite Co., Ltd., product name "053-40DU", expansion start temperature (t) = 100 ° C.

In Production Examples 2 and 3, when forming the support layer (II) forming sheet, the drying temperature after applying the resin composition to form the coating film is set to the expansion start temperature of the heat-expandable particles (the expansion start temperature). Although it is higher than t), since the above-mentioned drying temperature is the ambient temperature, no foaming was observed in the formed support layer (II).

Manufacturing example 4
(Support layer (II-D))
In Production Example 1, the heat-expandable particles A were changed to the following heat-expandable particles D, and the drying conditions after applying the resin composition to form a coating film were changed to 1 minute at an atmospheric temperature of 100 ° C. A sheet for forming a support layer (II-D) was produced in the same manner as in Production Example 1 except for the above.
-Thermal expandable particles D: manufactured by Nippon Phillite Co., Ltd., product name "920-40DU", expansion start temperature (t) = 120 ° C.

[Preparation of sheet for forming curable resin layer (I)]
Production example 5
(Energy ray curable resin layer (IA))
Each component of the type and blending amount (all "active ingredient ratio") shown below is blended, further diluted with methyl ethyl ketone, and uniformly stirred to have a curable composition having a solid content concentration (active ingredient concentration) of 61% by mass. A solution of the substance was prepared.
[(A2) component]
-Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA"): 17.6 parts by mass [(b) component]
Acrylic polymers: 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 (20 parts by mass). Acrylic resin obtained by copolymerizing HEA) (15 parts by mass) (glass transition temperature: −28 ° C., Mw: 800,000): 17 parts by mass [component (c)]
-Phenyl1-hydroxycyclohexyl ketone (manufactured by BASF, product name "IRGACURE-184"): 0.5 parts by mass [component (d)]
-Epoxy group-containing oligomer-type silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"): 0.6 parts by mass [component (e)]
-TDI-based cross-linking agent (Toyochem Co., Ltd., product name "BHS-8515"): 0.5 parts by mass [(f) component]
・ 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. g) Ingredients]
-Imidazole (manufactured by Shikoku Chemicals Corporation, product name "2PH-Z"): 1.5 parts by mass

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

Production example 6
(Energy ray curable resin layer (IB))
Each component of the type and blending amount (all "active ingredient ratio") shown below is blended, further diluted with methyl ethyl ketone, and uniformly stirred to have a curable composition having a solid content concentration (active ingredient concentration) of 61% by mass. A solution of the substance was prepared.
[(A2) component]
Ε-Caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name "A-9300-1CL", trifunctional UV curable compound): 10 parts by mass [(b) component]
-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 [(c) component ]
2- (Dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (manufactured by BASF, product name "Irgacure (registered trademark) 369"): 0.6 parts by mass [(d) component]
3-Methylmethacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-503"): 0.4 parts by mass [(h) component]
-Silica filler (molten quartz filler, average particle size 8 μm): 57 parts by mass [(z) component]
-Mix 32 parts by mass of phthalocyanine blue dye (Pigment Blue 15: 3), 18 parts by mass of isoindolinone yellow dye (Pigment Yellow 139), and 50 parts by mass of anthraquinone red dye (Pigment Red 177). Pigment obtained by pigmenting so that the total amount of the above three types of dyes / the amount of styrene acrylic resin = 1/3 (mass ratio): 4 parts by mass

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

Production example 7
(Thermosetting resin layer (IC))
Each component of the type and blending amount (all "active ingredient ratio") shown below is blended, further diluted with methylethic ketone, stirred uniformly, and cured with a solid content concentration (active ingredient concentration) of 61% by mass. A solution of the sex composition was prepared.
Acrylic polymers: 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 (15 parts by mass). Acrylic resin obtained by copolymerizing 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 Co., Ltd., 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" Adecab Donner 3636AS "): 0.5 parts by mass, imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name" 2PH-Z " ): 0.5 parts by mass, epoxy group-containing oligomer-type silane coupling agent (manufactured by Mitsubishi Chemical Co., Ltd., 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 is applied onto the peeling-treated surface of the light release film to form a coating film, and the coating film is dried at 120 ° C. for 2 minutes and thermoset to a thickness of 25 μm. A thermosetting resin layer (IC) was formed, and a thermosetting resin layer (IC) forming sheet composed of a thermosetting resin layer (IC) and a light release film was prepared.

[Preparation of laminate]
Examples 1-5, Reference Example 1
The heavy release film of the support layer (II) forming sheet shown in Table 1 was removed, and the curability of the exposed first adhesive layer (X1) and the curable resin layer (I) forming sheet shown in Table 1 was removed. The surface of the resin layer (I) was bonded to obtain a laminate. In Example 5, the product name “Riva Alpha 3195” (expansion start temperature (t) = 170 ° C.) manufactured by Nitto Denko KK was used as the support layer (II-E) forming sheet.
Table 1 shows the evaluation results of the separability and warpage of the laminate obtained in each example.

[Preparation of cured sealant]
Subsequently, using the laminates obtained in each example, a cured sealed body was produced by the following procedure.

(1) The light release film on the support layer (II) side of the mounting laminate of the semiconductor chip is removed, and the adhesive surface of the second adhesive layer (X2) of the exposed support layer (II) is used as a support (1). Glass) and pasted.
Then, the light release film on the curable resin layer (I) side was also removed, and nine semiconductor chips (each chip size was 6.4 mm × 6.) were placed on the surface of the exposed curable resin layer (I). 4 mm, chip thickness 200 μm (# 2000)) was placed at necessary intervals so that the back surface of each semiconductor chip opposite to the circuit surface was in contact with the surface of the curable resin layer (I). ..

(2) Formation of Curable Resin Layer (I') In Examples 1 to 5, the energy ray-curable resin layer which is the curable resin layer (I) is after the above (1) and before the following (3). (I) was irradiated with ultraviolet rays (UV) to form a cured resin layer (I') on which a semiconductor chip was placed. The ultraviolet rays were irradiated from the support (glass) side three times using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Corporation) under the conditions of ^{an illuminance of 215 mW / cm 2} and a light intensity of 187 mJ / cm ^2.
In Reference Example 1, (2) was not carried out, and in (3) described later, 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 Cured Sealed Body The nine above-mentioned semiconductor chips and the surface of the cured resin layer (I') (thermosetting resin layer in Reference Example 1) at least in the peripheral portion of the semiconductor chip are sealed. It is coated with a thermosetting sealing resin film, which is a stop material, and the sealing resin film is heat-cured using a vacuum heating and pressurizing laminator (manufactured by ROHM and HAAS, product name "7024HP5") to cure and seal. A stop was made. The sealing conditions are as follows.
・ Preheating temperature: 100 ° C for both table and diaphragm
・ Evacuation: 60 seconds ・ Dynamic press mode: 30 seconds ・ Static press mode: 10 seconds ・ Sealing temperature: 180 ° C x 60 minutes

(4) Separation at interface P After the above (3), thermal expansion treatment is performed for 3 minutes at the expansion start temperature (t) + 30 ° C. of the heat-expandable particles contained in the support layer (II) of each laminate. Was separated at the interface P between the first pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I'). As a result, a cured encapsulant with a cured resin layer was obtained.

From Table 1, in Examples 1 to 5 using the laminated body which is one aspect of the present invention, the formed cured sealing body does not warp and the support layer (II) is excellent in separability. rice field.
On the other hand, in Reference Example 1 in which the thermosetting resin layer was used as the curable resin layer, the support layer (II) could not be separated from the curable resin layer (I').

1a, 1b, 2a, 2b, 3 laminated body (I) Energy ray curable resin layer (I') Cured resin layer (II) Support layer (X) Adhesive layer (X1) First adhesive layer (X2) First 2 Adhesive layer (Y) Base material (Y1) Expandable base material layer (Y2) Non-expandable base material layer 50 Support 60 Encapsulation object (semiconductor chip)
70 Encapsulant 80 Curing encapsulant 100 Curing encapsulant 100a Curing encapsulant surface 110 Grinding means 200 Rewiring layer 300 External terminal electrode

Claims (11)

Energy ray curable resin layer (I) and
It has a support layer (II) that supports the energy ray-curable resin layer (I), and has.
The energy ray curable resin layer (I) has a sticky surface and
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 heat-expandable particles.
A laminate in which a cured resin layer (I') formed by curing an energy ray-curable resin layer (I) and a support layer (II) are separated at an interface by a treatment for expanding the heat-expandable particles. Claimed that the storage elastic modulus E'at 23 ° C. of the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) is 1.0 × 10 ^{7 to} 1.0 × 10 ¹³ Pa. Item 1. The laminated body according to Item 1. The laminate according to claim 1 or 2, wherein the energy ray-curable resin layer (I) has a thickness of 1 to 500 μm. The laminate according to any one of claims 1 to 3, wherein the energy ray-curable resin layer (I) has a visible light transmittance of 5% or more. The laminate according to any one of claims 1 to 4, wherein the base material (Y) has an expandable base material layer (Y1) containing the heat-expandable particles. The laminate according to claim 5, wherein the pressure-sensitive adhesive layer (X) is a non-expandable pressure-sensitive adhesive layer. The laminate according to claim 5 or 6, wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated. The base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1).
The support layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X) in this order.
The laminate according to any one of claims 5 to 7, wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated. 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).
The object to be sealed and the surface of the cured resin layer (I') at least in the peripheral portion of the object to be sealed are coated 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 the treatment of expanding the thermally expandable particles, and the encapsulating object is separated. The laminate according to any one of claims 1 to 8, which is used for forming a cured encapsulating body containing the mixture. The laminate according to claim 9, which is used to prevent warpage of the cured sealant. A method for producing a cured encapsulant using the laminate according to any one of claims 1 to 10, wherein the cured encapsulant has the following steps (i) to (iv).
Step (i): Place the object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate Step (ii): On the energy ray-curable resin layer (I) Step of irradiating energy rays to form a cured resin layer (I') formed by curing the energy ray-curable resin layer (I) Step (iii): The encapsulation object and the encapsulation object At least the surface of the cured resin layer (I') in the peripheral portion is coated with a thermosetting encapsulant, and the encapsulant is thermosetting to form a cured encapsulant containing the encapsulating object. Step Step (iv): By the treatment of expanding the thermosetting particles, the cured resin layer (I') and the support layer (II) are separated at the interface thereof to obtain a cured sealing body with a cured resin layer. Process

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