JP7129110B2 - Laminate and method for producing cured sealing body - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a laminate and a cured sealing body.

2. Description of the Related Art In recent years, electronic devices have become smaller, lighter, and more functional, and semiconductor chips are sometimes mounted in packages close to their size. Such a package is sometimes called a CSP (Chip Scale Package). Examples of CSP include WLP (Wafer Level Package), which is completed by processing up to the final package process on a wafer size, and PLP (Panel Level Package), which is completed by processing up to the final package process on 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"), a semiconductor chip is covered with a sealing material so as to have a region larger than the chip size, and the semiconductor chip is formed. Then, a rewiring layer and external electrodes are formed not only on the circuit surface of the semiconductor chip but also on the surface region of the encapsulant.

FOWLP and FOPLP include, for example, a mounting process of mounting a plurality of semiconductor chips on a temporary fixing sheet, a coating process of coating with a thermosetting sealing material, and a thermosetting of the sealing material to cure it. A curing step of obtaining a sealing body, a separation step of separating the cured sealing body and the temporary fixing sheet, and a rewiring layer forming step of forming a rewiring layer on the exposed semiconductor chip side surface. (Hereinafter, the processing performed in the coating step and the curing step is also referred to as “sealing processing”).

Patent Literature 1 discloses a heat-peelable 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 side of a base material. It is also conceivable to use the heat-peelable pressure-sensitive adhesive sheet described in Patent Document 1 in the production of FOWLP and FOPLP.

Japanese Patent No. 3594853

However, when the adhesive sheet described in Patent Literature 1 is used as a temporary fixing sheet to produce a cured sealant, the cured sealant tends to warp due to heat shrinkage. This is because the semiconductor chips sealed in the hardened encapsulant are biased toward the surface side in contact with the temporary fixing sheet, so the presence of semiconductor chips with a small thermal expansion coefficient in the hardened encapsulant. A region with a relatively high ratio and a region with a relatively high proportion of cured resin with a large thermal expansion coefficient are generated, and stress is generated due to the difference in thermal contraction rate between the two regions. Conceivable. This problem tends to become more pronounced as package sizes such as FOWLP and FOPLP increase.
A warped hardened sealing body is likely to crack, for example, when the hardened sealing body is ground in the next process. There may be adverse effects such as troubles easily occurring at the time of delivery of the body.

As a method for suppressing the warp of the cured sealing body, for example, a method of using a laminate including a temporary fixing layer provided with a thermally expandable adhesive layer containing thermally expandable particles and a thermosetting resin layer may be considered. be done. That is, a semiconductor chip mounting step and a coating step are performed on the thermosetting resin layer provided in the laminate, and then the thermosetting resin layer and the sealing material are thermally cured to obtain a cured seal with a cured resin layer. In this method, after the stop body is obtained, the thermally expandable particles are foamed to separate the cured sealing body with the cured resin layer from the temporary fixing layer. According to this method, the cured resin layer functions as a warp-preventing layer of the cured sealing body, so that a cured sealing body in which warping is suppressed can be obtained.

On the other hand, according to the above method, since the treatment for foaming the thermally expandable particles and the treatment for curing the thermosetting resin layer are both heat treatments, the thermosetting resin layer is cured. The thermally expandable particles in the temporary fixing layer may foam during the heat treatment for the purpose. According to studies by the present inventors, if the thermally expandable particles in the temporary fixing layer are foamed before the thermosetting resin layer is sufficiently cured, the separability of the temporary fixing layer is deteriorated in the subsequent separation step. has been found.
Therefore, the cured resin layer and the temporary fixing layer can be easily separated after the cured sealing body with the cured resin layer is formed while the cured resin layer as the warpage prevention layer is applied to the cured sealing body. It would be desirable to have a laminate that can be used in the manufacture of cured encapsulants that is capable of producing curable encapsulants.

In view of the above problems, the present invention has a support layer and a curable resin layer, and can perform sealing by fixing an object to be sealed to the surface of the curable resin layer, and A laminate that can be provided with a cured resin layer as a warp prevention layer on a cured sealing body formed by processing and that can be easily separated from the cured resin layer and the support layer, and the laminate An object of the present invention is to provide a method for producing a hardened sealing body using

As a result of intensive studies aimed at solving the above problems, the present inventors have found that the above problems can be solved by the present invention described below, and have completed the present invention.
That is, the present invention relates to the following [1] to [11].
[1] 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 a sticky surface,
The support layer (II) has a substrate (Y) and an adhesive layer (X), at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles,
A laminate in which a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) and a support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles.
[2] The cured resin layer (I′) obtained by curing the energy ray-curable resin layer (I) has a storage elastic modulus E′ at 23° C. of 1.0×10 ⁷ to 1.0×10 ¹³ Pa. The laminate according to [1] above.
[3] The laminate according to [1] or [2] above, wherein the energy ray-curable resin layer (I) has a thickness of 1 to 500 μm.
[4] The laminate according to any one of [1] to [3] above, wherein the energy ray-curable resin layer (I) has a visible light transmittance of 5% or more.
[5] The laminate according to any one of [1] to [4] above, wherein the substrate (Y) has an expandable substrate layer (Y1) containing the thermally expandable particles.
[6] The laminate according to [5] above, wherein the pressure-sensitive adhesive layer (X) is a non-expansive pressure-sensitive adhesive layer.
[7] The laminate according to [5] or [6] above, wherein the pressure-sensitive adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated.
[8] The substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1),
The support layer (II) has a non-expandable base layer (Y2), an expandable base 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] Placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I),
irradiating the energy ray-curable resin layer (I) with an energy ray to form a cured resin layer (I') by curing the energy ray-curable resin layer (I);
covering the object to be sealed and the surface of the cured resin layer (I′) at least in the periphery of the object to be sealed with a thermosetting sealing material;
After the sealing material is thermally cured, the cured resin layer (I′) and the support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles, and the sealing object is separated. The laminate according to any one of the above [1] to [8], which is used to form a cured sealing body containing.
[10] The laminate according to [9] above, which is used to prevent warping of the cured sealing body.
[11] A method for producing a cured sealant using the laminate according to any one of [1] to [10] above, comprising the following steps (i) to (iv): manufacturing method.
Step (i): A step of placing an object to be sealed on a portion 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 (iii) of forming a cured resin layer (I') by irradiating an energy ray to cure the energy ray-curable resin layer (I): the sealing object and the sealing object At least the surface of the cured resin layer (I') in the peripheral portion is coated with a thermosetting sealing material, and the sealing material is thermally cured to form a cured sealing body including the sealing object. Process step (iv): The cured resin layer (I′) and the support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles to obtain a cured sealant with a cured resin layer. process

ADVANTAGE OF THE INVENTION According to this invention, it has a support layer and a curable resin layer, can fix a sealing target to the surface of the said curable resin layer, and can perform a sealing process, and is formed by this sealing process. A laminate that can be provided with a cured resin layer as a warp prevention layer on a cured sealing body and that can be easily separated from the cured resin layer and the support layer, and curing using the laminate A method for manufacturing a sealing body can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body of the 1st aspect of this invention. It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body of the 2nd aspect of this invention. It is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body of the 3rd aspect of this invention. It is a cross-sectional schematic diagram which showed the process of manufacturing the cured sealing body with a cured resin layer using the laminated body 1a shown to Fig.1 (a). It is a cross-sectional schematic diagram which shows the processing method of a hardened sealant.

In the present specification, whether or not the target layer is a "non-expandable layer" is the volume change rate calculated from the following formula before and after the treatment for expansion after performing the treatment for 3 minutes. is less than 5%, the layer is judged to be a "non-intumescent layer." On the other hand, when the volume change rate is 5% or more, the layer is judged to be an "expandable layer".
・ Volume change rate (%) = {(volume of the layer after treatment - volume of the layer before treatment) / volume of the layer before treatment} x 100
As for the "treatment for expansion", for example, in the case of a layer containing thermally expandable particles, heat treatment may be performed for 3 minutes at the expansion start temperature (t) of the thermally expandable particles.

As used herein, the term “active ingredient” refers to the components contained in the target composition, excluding the diluent 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, specifically a value measured based on the method described in Examples. is.

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

In this specification, for preferred numerical ranges (for example, ranges of content etc.), the lower and upper limits described stepwise can be independently combined. For example, from the statement "preferably 10 to 90, more preferably 30 to 60", combining "preferred lower limit (10)" and "more preferred upper limit (60)" to "10 to 60" can also

Unless otherwise specified, each component and material exemplified in this specification may be used alone or in combination of two or more. When two or more are used in combination, combinations thereof and ratio can be selected arbitrarily.

As used herein, the term "energy ray" means an electromagnetic wave or charged particle beam that has energy quanta, and examples thereof include ultraviolet rays, radiation, electron beams, and the like. Ultraviolet rays can be applied 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 light source. The electron beam can be generated by an electron beam accelerator or the like.
As used herein, "energy ray-curable" means the property of curing by irradiation with energy rays, and "non-energy ray-curable" means the property of not curing even when irradiated with energy rays. do.

[Laminate]
A laminate of one embodiment 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 substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles.

The laminate of one embodiment of the present invention comprises a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) by a treatment for expanding the thermally expandable particles in the support layer (II), and a support layer (I'). Layer (II) can be separated at its interface. That is, in the laminate of one embodiment of the present invention, the heat expansion treatment causes the thermally expandable particles to expand, causing unevenness on the surface of the layer containing the thermally expandable particles. The contact area with the cured resin layer (I') formed by curing the flexible 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 collectively with a slight force.
In the laminate of one embodiment of the present invention, since it is not necessary to heat the energy ray-curable resin layer (I) when curing the energy ray-curable resin layer (I), the support layer The thermally expandable particles in (II) did not expand, and the separation between the support layer (II) and the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) was excellent. become a thing.

The laminate of one embodiment of the present invention is obtained by placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) and irradiating the energy ray-curable resin layer (I) with an energy ray. forming a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I), and forming the cured resin layer (I') on the object to be sealed and at least the periphery of the object to be sealed; The surface of the cured resin layer (I') and the support layer (II) are coated with a thermosetting sealing material, the sealing material is thermally cured, and then the thermally expandable particles are expanded. and are separated at their interface to form a hardened sealing body containing the sealing object.
The cured sealing body formed by the above method has the cured resin layer (I') on the surface of the side having a relatively high proportion of the semiconductor chips. As a result, the difference in shrinkage stress between the two surfaces of the hardened sealing body can be reduced, and a hardened sealing body in which warping is effectively suppressed can be obtained.
That is, the laminate of one embodiment of the present invention is useful as a warp-preventing laminate that is used to prevent warping of a cured sealant.
At that time, since the laminate of one embodiment of the present invention has the energy ray-curable resin layer (I) that is easier to adjust to increase the adhesive strength than the thermosetting resin layer, the sealing object is partially covered with the surface. can be fixed more securely. In addition, when the thermosetting resin layer is heated at a high temperature, it softens mainly in the initial stage of curing, which may lead to chip slippage. Since it is not softened by curing by irradiation, it is possible to avoid the occurrence of chip misalignment due to curing.

<Structure of laminate>
Next, the structure of the laminate of one embodiment of the present invention will be described with reference to the drawings.
1 to 3 are schematic cross-sectional views of laminates showing the configurations of laminates according to the first to third embodiments of the present invention. In the laminates of the following first to third aspects of the present invention, the adhesive surface of the adhesive layer (X) (or the second adhesive layer (X2)) to be attached to the support (i.e., the support and ) and the surface of the energy ray-curable resin layer (I) opposite to the support layer (II) side may be laminated with a release material.

[Laminate of first aspect]
As the laminate of the first aspect of the present invention, laminates 1a and 1b shown in FIG. 1 are exemplified.
The laminates 1a and 1b each include an energy ray-curable resin layer (I), a support layer (II) having a base material (Y) and an adhesive layer (X), and a base material (Y) and an energy It has a structure in which the linear curable resin layer (I) is directly laminated.
In addition, in the laminate of the first aspect of the present invention, the adhesive surface of the adhesive layer (X) is attached to a support (not shown).

The support layer (II) contains thermally expandable particles in at least one of the layers, and in the laminate 1a, the substrate (Y) is an expandable substrate layer containing thermally expandable particles ( It is a single-layer base material consisting only of Y1).
The base material (Y) may be a base material having a single-layer structure consisting only of the expandable base material layer (Y1), such as the laminate 1a shown in FIG. 1(a). Like the laminate 1b shown, the substrate may have a multi-layer structure having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2). When the substrate (Y) has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), the substrate (Y) comprises an expandable substrate layer (Y1) and a non-expandable substrate layer ( It may consist of only Y2).
Moreover, it is preferable that the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) are directly laminated.

In the laminate 1a shown in FIG. 1(a), the heat expansion treatment expands the thermally expandable particles contained in the expandable base material layer (Y1), causing irregularities on the surface of the base material (Y). The contact area with the cured resin layer (I') obtained by curing the linear curing resin layer (I) in advance is reduced.
At this time, the adhesive surface of the adhesive layer (X) is attached to a support (not shown). By attaching the pressure-sensitive adhesive layer (X) to the support so as to sufficiently adhere to the support, a force that causes unevenness is generated on the surface of the expandable substrate layer (Y1) on the pressure-sensitive adhesive layer (X) side. However, a repulsive force from the pressure-sensitive adhesive layer (X) is likely to occur. Therefore, irregularities are less likely to be formed on the surface of the substrate (Y) on the pressure-sensitive adhesive layer (X) side.
As a result, the laminate 1a can be easily separated collectively with a slight force at the interface P between the substrate (Y) of the support layer (II) and the cured resin layer (I').
It is also possible to make the separation at the interface P easier by forming the adhesive layer (X) of the laminate 1a from an adhesive composition having a high adhesive strength to the support.

From the viewpoint of suppressing the transmission of the stress due to the thermally expandable particles to the adhesive layer (X) side, the base material (Y) includes an expandable group, as in the laminate 1b shown in FIG. It preferably has a material layer (Y1) and a non-expandable substrate layer (Y2).
Since the stress due to the expansion of the thermally expandable particles in the expandable base layer (Y1) is suppressed by the non-expandable base layer (Y2), it is less likely to be transmitted to the pressure-sensitive adhesive layer (X).
Therefore, the surface of the pressure-sensitive adhesive layer (X) on the side of the support is less likely to become uneven, 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, unevenness is easily formed on the surface of the expandable substrate layer (Y1) on the side of the energy ray-curable resin layer (I), and as a result, the expandable substrate layer (Y1) of the support layer (II) and the curing At the interface P with the resin layer (I'), it becomes possible to easily separate them collectively with a slight force.
Note that, as in the laminate 1b shown in FIG. 1(b), the expandable substrate layer (Y1) and the energy ray-curable resin layer (I) are directly laminated, and the non-expandable substrate layer (Y2) is It is preferable that the pressure-sensitive adhesive layer (X) is laminated on the surface opposite to the expandable substrate layer (Y1).

[Laminate of Second Aspect]
Laminates 2a and 2b shown in FIG. 2 are examples of the laminate of the second aspect of the present invention.
In the laminates 2a and 2b, the pressure-sensitive adhesive layer (X) of the support layer (II) has the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), and the first pressure-sensitive adhesive layer (X1 ) and the second pressure-sensitive adhesive layer (X2), and the pressure-sensitive adhesive surface of the first pressure-sensitive adhesive layer (X1) is directly laminated to the energy ray-curable resin layer (I).
In addition, in the laminate 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, the substrate (Y) preferably has an expandable substrate layer (Y1) containing thermally expandable particles.
The substrate (Y) may be a substrate having a single-layer structure consisting of only the expandable substrate layer (Y1), such as the laminate 2a shown in FIG. 2(a). Like the laminate 2b shown, the substrate may have a multi-layer structure having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2).

However, as described above, from the viewpoint of obtaining a laminate that maintains good adhesion between the second pressure-sensitive adhesive layer (X2) and the support before and after the heat expansion treatment, as shown in FIG. The material (Y) preferably has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2).
In addition, in the laminate of the second mode, when the substrate (Y) having the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) is used, as shown in FIG. The first pressure-sensitive adhesive layer (X1) is laminated on the surface of the elastic base layer (Y1) on the energy ray-curable resin layer (I) side, and the expandable base layer of the non-expandable base layer (Y2) It is preferable to have a configuration in which a second pressure-sensitive adhesive layer (X2) is laminated on the surface opposite to (Y1).

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

[Laminate of the third aspect]
As the layered product of the third aspect of the present invention, a layered product 3 shown in FIG. 3 can be mentioned.
The laminate 3 shown in FIG. 3 has a first adhesive layer (X1), which is an expandable adhesive layer containing thermally expandable particles, on one surface side of the substrate (Y), and the substrate ( A support layer (II) having a second pressure-sensitive adhesive layer (X2) which is a non-expanding pressure-sensitive adhesive layer is provided on the other surface side of Y), the first pressure-sensitive adhesive layer (X1) and the energy ray-curable resin layer (I) and have a structure in which they are directly laminated.
In the laminate 3, the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown).
The substrate (Y) of the laminate of the third aspect of the present invention preferably comprises a non-expandable substrate layer.

In the laminate of the third aspect of the present invention, the thermal expansion treatment expands the thermally expandable particles in the first pressure-sensitive adhesive layer (X1), which is the expandable pressure-sensitive adhesive layer, 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') obtained by curing the energy ray-curable resin layer (I) in advance decreases.
On the other hand, since the base material (Y) is laminated on the surface of the first pressure-sensitive adhesive layer (X1) on the side of the base material (Y), irregularities are less likely to occur.
Therefore, due to the heat expansion treatment, irregularities are likely to be formed on the surface of the first pressure-sensitive adhesive layer (X1) on the side of the energy ray-curable resin layer (I), and as a result, the first pressure-sensitive adhesive layer ( At the interface P between X1) and the cured resin layer (I'), they can be easily separated collectively with a slight force.

The laminate of one embodiment of the present invention may consist of only the support layer (II) and the energy ray-curable resin layer (I), and the support layer (II) and the energy ray-curable resin layer (I) It may have layers other than the above. Examples of other layers include a pressure-sensitive adhesive layer provided on the surface of the energy ray-curable resin layer (I) opposite to the support layer (II).
In addition, the laminate of one embodiment of the present invention preferably does not have a thermosetting resin layer from the viewpoint of minimizing the need for heating in steps other than the thermal expansion treatment. However, the thermosetting resin layer here means a layer that is thermosetting and non-energy ray-curable.

<Various physical properties of the laminate>
(Peel force (F ₀ ))
Before the energy ray-curable resin layer (I) is cured and before the thermal expansion treatment, the object to be sealed is sufficiently fixed so as not to adversely affect the sealing work. It is preferable that the adhesiveness with the energy ray-curable resin layer (I) is high.
From the above viewpoint, in the laminate of one embodiment of the present invention, the support layer (II) and the energy ray-curable resin layer (I) before curing of the energy ray-curable resin layer (I) and before the heat expansion treatment are performed. The peel force (F ₀ ) when separating at the interface P with the It is below.
In addition, peeling force ( _F0 ) is a value measured by the following measuring method.
<Measurement of peel force (F ₀ )>
After the laminate was allowed to stand in an environment of 23° C. and 50% RH (relative humidity) for 24 hours, an adhesive tape (manufactured by Lintec Corporation, product name “PL Shin ”) is affixed.
Next, the support layer (II) side of the laminate is attached to a glass plate (manufactured by Yuko Shokai Co., Ltd., float plate glass, 3 mm (JISR 3202 product)) via an adhesive. Next, the end of the glass plate to which the laminate was attached is fixed to the lower chuck of a universal tensile tester (manufactured by Orientec Co., Ltd., product name “Tensilon UTM-4-100”).
Subsequently, the adhesive tape and the support layer (II) are fixed with an upper chuck of a universal tensile tester so that they are separated at the interface P between the support layer (II) and the energy ray-curable resin layer (I) of the laminate. . Then, under the same environment as above, based on JIS Z 0237: 2000, the peel force measured when peeled at the interface P at a tensile speed of 300 mm / min by a 180 ° peel method is referred to as "peeling force (F ₀ )”.

(Peel force (F ₁ ))
In the laminate of one embodiment of the present invention, after the energy ray-curable resin layer (I) is cured to form the cured resin layer (I′), the support layer (II) and the cured resin layer (I ') is usually 2000 mN _/ 25 mm or less, preferably 1000 mN/ It is 25 mm or less, more preferably 500 mN/25 mm or less, more preferably 150 mN/25 mm or less, even more preferably 100 mN/25 mm or less, even more preferably 50 mN/25 mm or less, most preferably 0 mN/25 mm.
When the peel force (F ₁ ) is 0 mN/25 mm, even if an attempt is made to measure the peel force, the measurement may not be possible because the peel force is too small.
In addition, peeling force (F1) is _a value measured by the following measuring method.
<Measurement of peel force (F ₁ )>
After the laminate is left to stand in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours, an adhesive tape (manufactured by Lintec Corporation, product name "PL Shin") is attached.
Next, the support layer (II) side of the laminate is attached to a glass plate (manufactured by Yuko Shokai Co., Ltd., float plate glass, 3 mm (JIS R 3202 product)) via an adhesive.
Next, ultraviolet light is applied three times under the conditions of an illuminance of 215 mW/cm ² and a light amount 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 laminate are heated at the maximum expansion temperature for 3 minutes to expand the thermally expandable particles in the expandable substrate layer (Y1) of the laminate. After that, in the same manner as the measurement of the peel force (F ₀ ) described above, the peel force measured when peeled at the interface P between the support layer (II) and the cured resin layer (I′) under the above conditions is It is referred to as “peeling force (F ₁ )”.
In the measurement of the peel force (F ₁ ), when the support layer (II) of the laminate was fixed with the upper chuck of the universal tensile tester, the cured resin layer (I') was completely separated at the interface P. If it is not fixed and the measurement is terminated, the peeling force (F ₁ ) at that time is set to "0 mN/25 mm".

(Adhesive strength of adhesive layer (X))
In the laminate of one embodiment of the present invention, the pressure-sensitive adhesive layer (X) (the first pressure-sensitive adhesive layer (X1) and the 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 ~4.0N/25mm.
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 respectively Although it is preferably within the above range, from the viewpoint of improving adhesion to the support and making it easier to separate collectively at the interface P, the thickness of the second pressure-sensitive adhesive layer (X2) attached to the support is increased. More preferably, the adhesive strength is higher than that of the first adhesive layer (X1).

(Adhesive strength of energy ray-curable resin layer (I))
In the laminate of one embodiment of the present invention, from the viewpoint of improving the adhesion to the object to be sealed, the energy ray-curable resin layer (I) is the surface on which the object to be sealed is placed (that is, The side opposite to the support layer (II)) has adhesiveness.
Specifically, at room temperature (23° C.), the adhesive strength of the surface of the energy ray-curable resin layer (I) on which the object to be sealed is placed is , preferably 0.05 N/25 mm or more, more preferably 0.10 N/25 mm or more, still more preferably 0.50 N/25 mm or more. The upper limit of the surface adhesive strength is not particularly limited, but is usually 50 N/25 mm or less, may be 40 N/25 mm or less, or may be 30 N/25 mm or less.

In addition, in this specification, these adhesive strengths are the values measured by the following measuring method.
<Measurement of adhesive strength>
A 50 μm-thick PET film (manufactured by Toyobo Co., Ltd., product name “Cosmoshine A4100”) is laminated on the surface of the 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) was attached to a stainless steel plate (SUS304, No. 360 polished) as an adherend, and the temperature was maintained at 23°C and 50% RH (relative humidity). After allowing to stand for 24 hours under the same environment, the adhesive force at 23° C. is measured at a pulling rate of 300 mm/min by the 180° peeling method in accordance with JIS Z0237:2000.

(Probe tack value of substrate (Y))
The substrate (Y) of the support layer (II) is a non-adhesive substrate.
In one aspect of the present invention, the determination of whether or not the substrate is non-adhesive is based on the surface of the target substrate having a probe tack value of less than 50 mN/5 mmφ measured in accordance with JISZ 0237:1991. If so, the substrate is judged to be a “non-adhesive substrate”. On the other hand, if the probe tack value is 50 mN/5 mmφ or more, the substrate is judged to be "adhesive substrate".
The probe tack value on the surface of the substrate (Y) of the support layer (II) used in one aspect of the present invention is usually less than 50 mN/5 mmφ, preferably less than 30 mN/5 mmφ, more preferably less than 10 mN/5 mmφ. , and more preferably less than 5 mN/5 mmφ.
The probe tack value on the surface of the substrate (Y) is a value measured by the following measuring method.
<Measurement of probe tack value>
A test sample is obtained by cutting a base material to be measured into a square having a side of 10 mm, and leaving the square 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), using a tacking tester (manufactured by Nihon Tokushu Sokki Co., Ltd., product name "NTS-4800"), the probe tack value on the surface of the test sample is measured according to JIS. Measure according to Z0237:1991. Specifically, a stainless steel probe with 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 moved at a speed of 10 mm/second to the test sample. The force required to remove it from the surface is measured and the resulting value is taken as the probe tack value for that test sample.

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

<Support layer (II)>
The support layer (II) included in the laminate of one embodiment of the present invention has a substrate (Y) and an adhesive layer (X), and at least one of the substrate (Y) and the adhesive layer (X) is It contains thermally 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 thermal expansion treatment, and serves as a so-called temporary fixing layer. .
The support layer (II) used in one embodiment of the present invention, depending on whether the layer containing thermally expandable particles is included in the structure of the base material (Y) or in the case of the pressure-sensitive adhesive layer (X). is divided into the following aspects.
- Support layer (II) of the first aspect: Support layer (II) comprising a substrate (Y) having an expandable substrate layer (Y1) containing thermally expandable particles.
- Support layer (II) of the second embodiment: a first pressure-sensitive adhesive layer (X1), which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles, and a non-expandable pressure-sensitive adhesive on both sides of the substrate (Y) A support layer (II) having a second adhesive layer (X2) which is a layer.

[Support layer (II) of the first embodiment]
As the support layer (II) of the first embodiment, as shown in FIGS. 1 and 2, the substrate (Y) has an expandable substrate layer (Y1) containing thermally expandable particles.
In the support layer (II) of the first embodiment, the pressure-sensitive adhesive layer (X) is preferably a non-expansive pressure-sensitive adhesive layer from the viewpoint of allowing easy separation 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-expanding pressure-sensitive adhesive layer.
In addition, in the support layer (II) of the laminates 2a and 2b shown in FIG. 2, both the first adhesive layer (X1) and the second adhesive layer (X2) are non-expansive adhesive layers. Preferably.
Since the substrate (Y) has the expandable substrate layer (Y1) as in the support layer (II) of the first embodiment, the pressure-sensitive adhesive layer (X) does not need to have expandability, and the adhesive layer (X) does not need to have expandability. It is not bound by composition, configuration and process for application. As a result, in designing the pressure-sensitive adhesive layer (X), for example, it is possible to design with priority given to desired performance other than expansibility, such as performance such as adhesiveness, productivity, and economic efficiency. The degree of design freedom of (X) can be improved.

The thickness of the substrate (Y) before the heat 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 μm. ~300 μm.

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

In this specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of adhesive layers (X), the above "thickness of the adhesive layer (X)" is It means the thickness of each pressure-sensitive adhesive layer (the thickness of each of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) in FIG. 2).
Moreover, in this specification, the thickness of each layer constituting the laminate means a value measured by the method described in Examples.

In the support layer (II) of the first aspect, the thickness ratio [(Y1)/(X)] between the expandable substrate layer (Y1) and the pressure-sensitive adhesive layer (X) before the thermal expansion treatment is: 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, a laminate that can be easily separated collectively with a slight force at the interface P between the support layer (II) and the cured resin layer (I′) by heat expansion treatment. 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.

In addition, in the support layer (II) of the first embodiment, the substrate (Y) may be composed only of the expandable substrate layer (Y1) as shown in FIG. 1(a), As shown in FIG. 1(b), an expandable substrate layer (Y1) is provided on the energy ray-curable resin layer (I) side, and a non-expandable substrate layer (Y2) is provided on the adhesive layer (X) side. It may have

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

[Support layer (II) of the second embodiment]
As the support layer (II) of the second embodiment, as shown in FIG. Examples include those having (X1) and a second pressure-sensitive adhesive layer (X2) which is a non-expanding pressure-sensitive adhesive layer.
In addition, in the support layer (II) of the second aspect, the first pressure-sensitive adhesive layer (X1), which is an expansive pressure-sensitive adhesive layer, and the energy ray-curable resin layer (I) are in direct contact.
In the support layer (II) of the second aspect, the substrate (Y) is preferably a non-expandable substrate. It is preferable that the non-expanding base material is composed only of the non-expanding base layer (Y2).

In the support layer (II) of the second embodiment, 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 respect to the thickness is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.

Further, in the support layer (II) of the second aspect, the thickness ratio [(X1) /(Y)] is preferably 0.05 to 20, more preferably 0.1 to 10, still more preferably 0.2 to 3.

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

[Thermal expandable particles]
As the thermally expandable particles used in one embodiment of the present invention, particles that expand by a predetermined thermal expansion treatment may be used.
The average particle size of the thermally expandable particles used in one aspect of the present invention before expansion at 23° C. is preferably 3 to 100 μm, more preferably 4 to 70 μm, even more preferably 6 to 60 μm, still more preferably 10 to 10 μm. 50 μm.
The average particle size of the thermally expandable particles before expansion is the volume-median particle size (D ₅₀ ), and is measured by a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern, product name "Mastersizer 3000"). In the particle distribution of the thermally expandable particles before expansion measured using , the particle size corresponding to a cumulative volume frequency of 50% calculated from the smallest particle size of the thermally expandable particles before expansion.

The 90% particle diameter (D ₉₀ ) before expansion at 23° C. of the thermally expandable particles used in one aspect of the present invention 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 diameter (D ₉₀ ) of the thermally expandable particles before expansion is measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern, product name “Mastersizer 3000”). In the particle distribution of the thermally expandable particles before expansion, it means a particle size corresponding to a cumulative volume frequency of 90% calculated from the smaller particle size of the thermally expandable particles before expansion.

The thermally expandable particles used in one aspect of the present invention may be particles that do not expand when the encapsulant is cured and have an expansion start temperature (t) higher than the curing temperature of the encapsulant. In particular, thermally expandable particles having an expansion start temperature (t) adjusted to 60 to 270°C are preferred. Note that the expansion start temperature (t) is appropriately selected according to the curing temperature of the sealing material used.
Further, in this specification, the expansion start temperature (t) of the thermally expandable particles means a value measured based on the method described in Examples.

The thermally expandable particles are microencapsulated foaming agents composed of an outer shell made of a thermoplastic resin and an encapsulated component that is encapsulated in the outer shell and vaporizes when heated to a predetermined temperature. Preferably.
Examples of thermoplastic resins constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.

Examples of encapsulated components encapsulated in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, and cyclopentane. , cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nanodecane, isotridecane, 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 thermally expandable particles can be adjusted by appropriately selecting the type of inclusion component.

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

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

In addition, from the viewpoint of improving the interlayer adhesion between the expandable base layer (Y1) and other layers to be laminated, the surface of the expandable base layer (Y1) is subjected to an oxidation method, a roughening method, or the like. A treatment, an easy-adhesion treatment, or a primer treatment may be applied.
Examples of oxidation methods include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of roughening methods include sandblasting and solvent treatment. etc.

In one aspect of the present invention, the expandable base layer (Y1) preferably satisfies the following requirement (1).
Requirement (1): The storage elastic modulus E'(t) of the expandable base material layer (Y1) at the expansion start temperature (t) of the thermally expandable particles is 1.0×10 ⁷ Pa or less.
In addition, in this specification, the storage elastic modulus E' of the expandable 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 indicating the rigidity of the expandable base material layer (Y1) immediately before the thermally expandable particles expand.
In order to make the interface P between the support layer (II) and the cured resin layer (I′) easily separable with a slight force, the support layer ( It is necessary to facilitate the formation of irregularities on the surface of II), which is laminated with the energy ray-curable resin layer (I).
That is, the expandable base material layer (Y1) satisfying the above requirement (1) becomes sufficiently large due to expansion of the thermally expandable particles at the expansion start temperature (t), and the energy ray-curable resin layer (I) is laminated. Concavities and convexities are likely to be formed on the surface of the support layer (II) on the side where the
As a result, 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') can be obtained.

The storage elastic modulus E′(t) of the expandable substrate layer (Y1) defined in 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, it suppresses the flow of the expanded thermally expandable particles, improves the shape retention 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, 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 expandable base layer (Y1) defined in requirement (1) is preferably 1.0× It is 10 ³ Pa or more, more preferably 1.0×10 ⁴ Pa or more, and still more preferably 1.0×10 ⁵ Pa or more.

The expandable substrate layer (Y1) is preferably formed from a resin composition (y) containing a resin and thermally expandable particles.
In addition, the resin composition (y) may contain additives for base materials, if necessary, as long as the effects of the present invention are not impaired.
Examples of base material additives include light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, colorants, and the like.
These base material additives may be used alone, or two or more of them may be used in combination.
When these base additives are contained, the content of each base additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 20 parts by mass, relative to 100 parts by mass of the resin. 10 parts by mass.

The content of the thermally expandable particles is preferably 1 to 40 with respect to the total amount (100% by mass) of the expandable substrate layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y). % 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 substrate layer (Y1), may be a non-adhesive resin or a tacky 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 substrate layer (Y1) from the resin composition (y). It is sufficient that the resin obtained by polymerization reaction with the compound becomes a non-adhesive resin, and the expandable substrate layer (Y1) containing the resin becomes non-adhesive.

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

Further, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and may be a block copolymer, a random copolymer, or a graft copolymer. 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 substrate layer (Y1) or the total amount (100% by mass) of the active ingredients of the resin composition (y). , more preferably 60 to 95 mass %, still more preferably 65 to 90 mass %, still more preferably 70 to 85 mass %.

From the viewpoint of forming the expandable substrate layer (Y1) that satisfies the requirement (1), the resin contained in the resin composition (y) is one selected from acrylic urethane-based resins and olefin-based resins. It is preferred to contain more than one seed.
Moreover, as the acrylic urethane-based resin, the following resin (U1) is preferable.
• An 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 forms the main chain of the acrylic urethane resin (U1) include reaction products of polyols and polyvalent isocyanates.
In addition, it is preferable that the urethane prepolymer (UP) is obtained by subjecting the urethane prepolymer (UP) to a chain extension reaction using a chain extension agent.

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

Examples of ester diols include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol; ethylene glycol, propylene glycol, 1 or 2 or more selected from diols such as alkylene glycols such as diethylene glycol and dipropylene glycol; ,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, het acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexa Condensation products of one or more selected from dicarboxylic acids such as hydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, and anhydrides thereof may be mentioned.
Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, 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 pentyl terephthalate diol and the like.

Examples of alkylene type diols include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol; ethylene glycol, propylene glycol, alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol;

Examples of carbonate-type diols include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-propylene carbonate diol, 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.

Aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like are examples of polyvalent isocyanates that are raw materials for urethane prepolymers (UP).
These polyvalent isocyanates may be used alone or in combination of two or more.
Further, these polyvalent isocyanates may be trimethylolpropane adduct-type modified products, biuret-type modified products reacted with water, and isocyanurate-type modified products containing an isocyanurate ring.

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

Alicyclic diisocyanates include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane Examples include diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, and isophorone diisocyanate (IPDI) is preferred.

In one aspect of the present invention, the urethane prepolymer (UP) that forms 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 for introducing ethylenically unsaturated groups at both ends of the linear urethane prepolymer, an NCO group at the terminal of the linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth)acrylate and a method of reacting with.

Hydroxyalkyl (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxy Butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like can be mentioned.

The vinyl compound that becomes 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)acrylates and hydroxyalkyl (meth)acrylates are preferable, and it is more preferable to use alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates together.

When alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate are used in combination, the ratio of hydroxyalkyl (meth)acrylate to 100 parts by mass of alkyl (meth)acrylate is preferably 0.1 to 100 parts by mass, more 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 number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1-24, more preferably 1-12, even more preferably 1-8, and even more preferably 1-3.

Examples of hydroxyalkyl (meth)acrylates include the same hydroxyalkyl (meth)acrylates used for introducing ethylenically unsaturated groups to both ends of the linear urethane prepolymer described above.

Examples of vinyl compounds other than (meth)acrylic esters include aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate. , (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, meta(acrylamide) and other polar group-containing monomers;
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, and still more preferably 80 to 100% by mass, more preferably 90 to 100% by mass.

The total content of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate in the vinyl compound is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, based on the total amount (100% by mass) of the vinyl compound. 100% by mass, more preferably 80 to 100% by mass, 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, still more preferably 35 /65 to 55/45.

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

Specific olefin resins include, for example, ultra-low density polyethylene (VLDPE, density: 880 kg/m ³ or more and less than 910 kg/m ³ ), low density polyethylene (LDPE, density: 910 kg/m ³ or more and less than 915 kg/m 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), polyethylene resin such as linear low density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymer (EVA); vinyl alcohol copolymers (EVOH); olefinic terpolymers such as ethylene-propylene-(5-ethylidene-2-norbornene);

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

For example, the acid-modified olefin resin obtained by subjecting an olefin resin to acid modification is a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or its anhydride to the above-described unmodified olefin resin. are mentioned.
Examples of unsaturated carboxylic acids or anhydrides thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, and itaconic anhydride. , glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride and the like.
The unsaturated carboxylic acid or its anhydride may be used alone, or two or more of them may be used in combination.

The acrylic-modified olefin-based resin obtained by subjecting an olefin-based resin to acrylic modification includes modification obtained by graft-polymerizing an alkyl (meth)acrylate as a side chain to the above-described unmodified olefin-based resin that is the main chain. polymers.
The number of carbon atoms in the alkyl group of the above alkyl (meth)acrylate is preferably 1-20, more preferably 1-16, still more preferably 1-12.
Examples of the above alkyl (meth)acrylates include the same compounds as those that can be selected as the monomer (a1') described below.

Examples of the hydroxyl group-modified olefin resin obtained by modifying the olefin resin with hydroxyl groups include a modified polymer obtained by graft polymerizing a hydroxyl group-containing compound to the above-described unmodified olefin resin that is the main chain.
Examples of the above hydroxyl group-containing compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl hydroxyalkyl (meth)acrylates such as (meth)acrylate and 4-hydroxybutyl (meth)acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.

(Resins other than acrylic urethane resins and olefin resins)
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 copolymer; Coalescence; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resins; polysulfone; polyetheretherketone; polyethersulfone; polyphenylene sulfide; Fluorinated resins and the like are included.

However, from the viewpoint of forming the expandable base layer (Y1) that satisfies the above requirement (1), the content of the resin other than the acrylic urethane resin and the olefin resin in the resin composition (y) should be as small as possible. preferable.
The content 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 resin contained in the resin composition (y). less than 10 parts by weight, more preferably less than 5 parts by weight, and even more preferably less than 1 part by weight.

(Solvent-free resin composition (y1))
As the resin composition (y) used in one aspect of the present invention, an oligomer having an ethylenically unsaturated group with a mass average molecular weight (Mw) of 50000 or less, an energy ray-polymerizable monomer, and the above-described thermally expandable particles are blended. and a solvent-free resin composition (y1) containing no solvent.
The solvent-free resin composition (y1) does not contain a solvent, but the energy ray-polymerizable monomer contributes to improving 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 the expandable substrate layer (Y1) that satisfies the requirement (1).

The type, shape and compounding amount (content) of the thermally expandable particles to be compounded in the solvent-free resin composition (y1) are as described above.

The weight average molecular weight (Mw) of the oligomer contained in the solventless resin composition (y1) is 50000 or less, preferably 1000 to 50000, more preferably 2000 to 40000, still more preferably 3000 to 35000, Even more preferably 4000 to 30000.

Further, as the oligomer, among the resins contained in the above resin composition (y), those having an ethylenically unsaturated group with a mass average molecular weight of 50000 or less may be used, but the above urethane prepolymer ( UP) is preferred.
A modified olefinic resin having an ethylenically unsaturated group can also be used as the oligomer.

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

Energy beam-polymerizable monomers include, for example, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, cyclohexyl (meth)acrylate, adamantane ( Alicyclic polymerizable compounds such as meth) acrylate and tricyclodecane acrylate; Aromatic polymerizable compounds such as phenylhydroxypropyl acrylate, benzyl acrylate, and phenol ethylene oxide-modified acrylate; Examples 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 blending ratio of the oligomer and the energy ray polymerizable monomer (the oligomer/energy ray polymerizable monomer) is preferably 20/80 to 90/10, more preferably 30/70 to 85/15, still more preferably 35/65. ~80/20.

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

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

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

<Non-expandable base layer (Y2)>
Examples of the material for forming the non-expanding base layer (Y2) that constitutes the base (Y) include paper materials, resins, metals, etc., and are appropriately selected according to the application of the laminate of one embodiment of the present invention. can be selected.

Examples of the paper material include thin paper, medium quality paper, fine paper, impregnated paper, coated paper, art paper, parchment paper, and glassine paper.
Examples of resins include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as butylene terephthalate and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyether sulfone; polyphenylene sulfide; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resins; acrylic resins;
Examples of metals include aluminum, tin, chromium, and titanium.

These forming materials may be composed of one type, or two or more types may be used in combination.
The non-expanding base material layer (Y2) using two or more kinds of forming materials in combination includes a paper material laminated with a thermoplastic resin such as polyethylene, a resin film or sheet containing a resin, and a metal film formed on the surface of the sheet. and the like.
As a method for forming the metal layer, for example, the above metal is deposited by a PVD method such as vacuum deposition, sputtering, or ion plating, or a metal foil made of the above metal is attached using a general adhesive. and the like.

Here, in one aspect of the present invention, when the expandable particles contained in the expandable base layer (Y1) are expanded, the non-expandable base layer (Y2) side of the expandable base layer (Y1) From the viewpoint of suppressing the formation of unevenness on the surface and predominantly forming unevenness on the surface of the expandable substrate layer (Y1) on the pressure-sensitive adhesive layer (X1) side, the non-expandable substrate layer ( Y2) preferably has such rigidity that it does not deform due to the expansion of the expandable particles. Specifically, the storage elastic modulus E′(t) of the non-expandable base layer (Y2) at the temperature (t) at which the expandable particles start to expand is 1.1×10 ⁷ Pa or more. is preferred.

From the viewpoint of improving the interlayer adhesion between the non-expanding base layer (Y2) and other layers to be laminated, when the non-expanding base layer (Y2) contains a resin, the non-expanding base layer The surface of (Y2) may also be subjected to a surface treatment such as an oxidation method or roughening method, an adhesion-facilitating treatment, or a primer treatment, as in the case of the expandable base layer (Y1) described above.

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

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

In addition, the non-expandable base layer (Y2) may contain thermally expandable particles as long as the volume change rate is within the above range. For example, by selecting a resin to be contained in the non-expandable base layer (Y2), even if thermally expandable particles are contained, the volume change rate can be adjusted within the above range.
However, the non-expandable base layer (Y2) preferably does not contain thermally expandable particles. When the non-expandable base layer (Y2) contains thermally expandable particles, the content thereof is preferably as small as possible. Generally 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 0.01% by mass, relative to the total amount (100% by mass) of 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.
Moreover, the pressure-sensitive adhesive composition (x) may contain additives for pressure-sensitive adhesive such as a cross-linking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary.
Each component contained in the pressure-sensitive adhesive composition (x) will be described below.
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) , can be formed from a pressure-sensitive adhesive composition (x) containing each component shown below.

(adhesive resin)
As the adhesive resin used in one aspect of the present invention, it is preferable that the resin alone has adhesiveness and is a polymer having a mass average molecular weight (Mw) of 10,000 or more.
The mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and still more preferably 30,000 from the viewpoint of improving adhesive strength. ~1 million.

Examples of specific adhesive resins include acrylic resins, urethane resins, rubber resins such as 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.
In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, and may be block copolymers, random copolymers, and graft copolymers. Any polymer may be used.

In one aspect of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive strength.
When using the support layer (II) having the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), the first pressure-sensitive adhesive layer ( By including an acrylic resin in X1), it is possible to facilitate the formation of unevenness on the surface of the first pressure-sensitive adhesive layer (X1).

The content 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). 100 mass %, more preferably 50 to 100 mass %, still more preferably 70 to 100 mass %, still more preferably 85 to 100 mass %.

The content of the adhesive resin is preferably 35 to 100 mass with respect to the total amount (100 mass%) of the active ingredients of the adhesive composition (x) or the total amount (100 mass%) of the adhesive layer (X). %, more preferably 50 to 100 mass %, still more preferably 60 to 98 mass %, still more preferably 70 to 95 mass %.

(crosslinking agent)
In one 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 the adhesive resin having a functional group to cross-link the adhesive resins with the functional group as a cross-linking starting point.

Examples of cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, and metal chelate-based cross-linking agents.
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 preferred from the viewpoints of increasing cohesive strength and improving adhesive strength, and from the viewpoint of availability and the like.

The content of the cross-linking agent is appropriately adjusted according to the number of functional groups possessed by the adhesive resin. More preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 5 parts by mass.

(Tackifier)
In one aspect of the present invention, the pressure-sensitive adhesive composition (x) may further contain a tackifier from the viewpoint of further improving the adhesive strength.
As used herein, the term "tackifier" refers to a component that supplementarily improves the adhesive strength of the adhesive resin described above, and refers to an oligomer having a weight average molecular weight (Mw) of less than 10,000. It is distinguished from the synthetic resin.
The weight average molecular weight (Mw) of the tackifier is preferably 400-9000, more preferably 500-8000, still more preferably 800-5000.

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

The softening point of the tackifier is preferably 60 to 170°C, more preferably 65 to 160°C, still more preferably 70 to 150°C.
In addition, in this specification, the "softening point" of a tackifier means the value measured based on JISK2531.
The tackifiers may be used alone, or two or more of them having different softening points, structures, etc. may be used in combination.
When two or more tackifiers are used, the weighted average of the softening points of the tackifiers preferably falls within 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 ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X). % 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.

(Adhesive additive)
In one aspect of the present invention, the pressure-sensitive adhesive composition (x) contains additives for pressure-sensitive adhesives that are commonly used for pressure-sensitive adhesives, in addition to the above-described additives, within a range that does not impair the effects of the present invention. You may have
Examples of such adhesive additives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, and the like. are mentioned.
These adhesive additives may be used alone, or two or more of them may be used in combination.
When these adhesive additives are contained, the content of each adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001, per 100 parts by mass of the adhesive resin. ~10 parts by mass.

In addition, when using the support layer (II) of the above-described second embodiment having the first pressure-sensitive adhesive layer (X1) which is an expansive pressure-sensitive adhesive layer, the first pressure-sensitive adhesive layer (X1) which is an expansive pressure-sensitive adhesive layer As the forming material, an expandable adhesive composition (x11) containing thermally expandable particles is used in addition to the above-described adhesive composition (x).
The thermally expandable particles are as described above.
The content of the thermally expandable particles is preferably 1 to 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-expanding pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition (x), which is the material for forming the non-expanding pressure-sensitive adhesive layer, preferably does not contain thermally expandable particles.
When containing thermally expandable particles, the content is preferably as small as possible, and the total amount (100% by mass) of the active ingredient of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X) %, preferably less than 1% by mass, more preferably less than 0.1% by mass, even more preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass.

In addition, 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-expanding pressure-sensitive adhesive layers, is used. In this case, the storage shear modulus G'(23) of the first pressure-sensitive adhesive layer (X1), which is a non-expanding pressure-sensitive adhesive layer, at 23°C is preferably 1.0 × 10 ⁸ Pa or less, more preferably 5.0 Pa or less. It is 0×10 ⁷ Pa or less, more preferably 1.0×10 ⁷ Pa or less.
If the storage shear modulus G′(23) of the first pressure-sensitive adhesive layer (X1), which is a non-expanding pressure-sensitive adhesive layer, is 1.0×10 ⁸ Pa or less, for example, laminates 2a and 2b shown in FIG. When configured as above, the first pressure-sensitive adhesive layer (X1 ) is likely to be uneven.
As a result, it is possible to obtain a laminate that can be easily separated collectively with a slight force at the interface P between the support layer (II) and the cured resin layer (I').
The storage shear modulus G'(23) of the first pressure-sensitive adhesive layer (X1), which is a non-expanding pressure-sensitive adhesive layer, at 23°C is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 Pa or more. It is 0×10 ⁴ Pa or more, more preferably 1.0×10 ⁵ Pa or more.

The support layer (II) included in the laminate of one embodiment of the present invention preferably has a light transmittance of 30% or higher, more preferably 50% or higher, and even more preferably 70% or higher at a wavelength of 375 nm. When the light transmittance is within the above range, when the energy ray-curable resin layer (I) is irradiated with energy rays (ultraviolet rays) through the support layer (II), the energy ray-curable resin layer (I) is cured. degree is improved. Although the upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, it 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 substrate (Y) and the pressure-sensitive adhesive layer (X) of the support layer (II) contain a colorant, It is preferable to adjust the content.
When a colorant is contained, the content thereof is preferably as small as possible. , 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 The content of the colorant is preferably less than 1% by mass, more preferably less than 1% by mass, relative to the total amount (100% by mass) of the active ingredients of the resin composition (y) or the total amount (100% by mass) of the substrate (Y). 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 irradiation with an energy ray. It 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 weight average molecular weight (Mw) of 80,000 to 2,000,000 (hereinafter also simply referred to as "polymer (a1)") , a compound (a2) having a molecular weight of 100 to 80,000 and having an energy ray-curable double bond (hereinafter also simply referred to as “compound (a2)”).
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 a weight average molecular weight (Mw) of 80,000 to 2,000,000.
Examples of the polymer (a1) include an acrylic polymer (a11) having a functional group X reactive with a group possessed by another compound, a group Y reactive with the functional group X, and an energy ray-curable double polymer (a11). An energy ray-curable compound (a12) having a bond and an acrylic resin (a1-1) obtained by polymerization can be mentioned.
Polymer (a1) may be used alone or in combination of two or more.

- Acrylic polymer (a11)
Examples of the functional group X possessed by the acrylic polymer (a11) include a hydroxyl group, a carboxyl 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 a hydrogen atom). group) and one or more selected from the group consisting of 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 not having the functional group X. In addition to these monomers, Furthermore, monomers other than acrylic monomers (non-acrylic monomers) 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 acrylic monomers having the functional group X include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, substituted amino group-containing monomers, and epoxy group-containing monomers.
Examples of hydroxyl group-containing monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acryl Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acid, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; non-(meth)acrylic unsaturated compounds such as vinyl alcohol and allyl alcohol alcohol (unsaturated alcohol having no (meth)acryloyl skeleton) and the like.
Examples of carboxy group-containing monomers include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, citraconic acid; ethylenically unsaturated dicarboxylic acid (dicarboxylic acid having an ethylenically unsaturated bond); anhydride of the ethylenically unsaturated dicarboxylic acid; (meth)acrylic acid carboxyalkyl ester such as 2-carboxyethyl methacrylate; .
Among these, hydroxyl group-containing monomers and carboxy group-containing monomers are preferable, and hydroxyl group-containing monomers are more preferable.

Examples of acrylic monomers having no functional group X include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 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 (meth) acrylate), tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, ( Alkyl groups constituting alkyl esters such as hexadecyl methacrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate) have a carbon number of Examples thereof include (meth)acrylic acid alkyl esters having a chain structure of 1 to 18.
Examples of acrylic monomers having no functional group X include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and the like. Alkoxyalkyl group-containing (meth) acrylic acid esters; (meth) acrylic acid esters having an aromatic group, including (meth) acrylic acid aryl esters such as phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; (meth)acrylic acid esters having non-crosslinkable tertiary amino groups such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; mentioned.
Examples of the non-acrylic monomers 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, relative to the total amount of the structural units constituting the acrylic 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 within the above range, the content of energy ray-curable double bonds in the resulting acrylic resin (a1-1) can be easily adjusted within a preferred 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, the isocyanate group is preferred. When the energy ray-curable compound (a12) has an isocyanate group, this isocyanate group readily 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 possessed by the energy ray-curable compound (a12) is preferably 1 to 5, more preferably 1 to 3, per 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, 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, a polyol compound, and hydroxyethyl (meth) acrylate and acryloyl monoisocyanate compounds that can be used. Among these, 2-methacryloyloxyethyl isocyanate is preferred.

In the acrylic resin (a1-1), the content of energy ray-curable double bonds derived from the energy ray-curable compound (a12) with respect to the content of the functional group X derived from the acrylic polymer (a11) is preferably 20 to 120 mol %, more preferably 5 to 100 mol %, still more preferably 50 to 100 mol %. When the ratio is within the above range, the adhesive strength of the cured resin layer (I') formed by curing is increased. When the energy ray-curable compound (a12) is a monofunctional compound (having one of the above groups in one molecule), the upper limit of the content ratio is 100 mol%. 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 ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and still more preferably 3 to 20% by mass.

The mass average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.

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

(Compound (a2))
Compound (a2) is a compound having an energy ray-curable double bond and 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 low molecular weight compounds having an energy ray-curable double bond, epoxy resins having an energy ray-curable double bond, and phenolic resins having an energy ray-curable double bond. .
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 preferred.
Examples of acrylate compounds include 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4- ((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[ 4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecanedimethanol di(meth)acrylate (tricyclo Decanedimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate (meth)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)isocyanate Nurate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra Polyfunctional (meth)acrylates such as (meth)acrylates, dipentaerythritol poly(meth)acrylates, dipentaerythritol hexa(meth)acrylates; urethane (meth)acrylates; Examples include polyfunctional (meth)acrylate oligomers such as ligomers.

As the epoxy resin having an energy ray-curable double bond and the phenolic resin having an energy ray-curable double bond, for example, those described in paragraph 0043 of Japanese Patent Application Laid-Open No. 2013-194102 are used. be able to. Such a resin also corresponds to a resin constituting a 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 ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 20% by mass.

[Polymer (b) having no energy ray-curable double bond]
When the energy ray-curable resin composition contains the compound (a2), it further contains a polymer (b) having no energy ray-curable double bond (hereinafter also simply referred to as "polymer (b)"). preferably.
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, and polyester urethane resins. Among these, an acrylic polymer (hereinafter also referred to as “acrylic polymer (b-1)”) is preferred.

The acrylic polymer (b-1) may be a known one, and may be, for example, a homopolymer of one acrylic monomer or a copolymer of two or more acrylic monomers. Alternatively, it may be a copolymer of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

Examples of acrylic monomers constituting the acrylic polymer (b-1) include (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having a cyclic skeleton, glycidyl group-containing (meth)acrylic acid esters, and hydroxyl groups. Containing (meth)acrylic acid esters, substituted amino group-containing (meth)acrylic acid esters, and the like can be mentioned. Here, the "substituted amino group" is as described above.

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

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

Examples of glycidyl group-containing (meth)acrylic acid esters include glycidyl (meth)acrylate.
Examples of hydroxyl group-containing (meth)acrylic acid esters 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.
Substituted amino group-containing (meth)acrylic acid esters include, for example, N-methylaminoethyl (meth)acrylate.

Examples of non-acrylic monomers constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

At least a portion of the polymer (b) may be crosslinked by the crosslinking agent (e), or may be non-crosslinked.
Examples of the polymer (b) at least partially crosslinked by the crosslinking agent (e) include those in which the reactive functional groups in the polymer (b) have reacted with the crosslinking agent (e).
The reactive functional group may be appropriately selected according to the type of the cross-linking agent (e), etc., and is not particularly limited. For example, when the cross-linking agent (e) is a polyisocyanate compound, the reactive functional group includes, for example, a hydroxyl group, a carboxyl group, an amino group, and the like. High hydroxyl groups are preferred. When the cross-linking agent (e) is an epoxy-based compound, examples of the reactive functional group include a carboxy group, an amino group, an amide group, and the like. A carboxyl group with a high is preferred. However, from the viewpoint of preventing corrosion of the circuits of the semiconductor wafer and semiconductor chip, the reactive functional group is preferably a group other than the carboxyl group.

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

In the polymer (b), the content of structural units derived from a 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 structural units constituting the polymer (b). be. When the content of the structural unit is within 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 from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000, from the viewpoint of better film-forming properties 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). When the compound (a2) is contained, the polymer (b) is also used. It is preferable to contain.

The total content of the energy ray-curable component (a) and the polymer (b) is the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount of the energy ray-curable resin layer (I) ( 100% by mass), preferably 5 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 15 to 70% by mass. If the total content is within the above range, the energy ray curability will be 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 It is preferably 3 to 160 parts by mass, more preferably 6 to 130 parts by mass, per 100 parts by mass of the chemical component (a). When the content of the polymer (b) is within the above range, the energy ray curability becomes better.

The energy ray-curable resin composition contains, in addition to the energy ray-curable component (a) and the polymer (b), a photopolymerization initiator (c), a coupling agent (d), a cross-linking agent (e ), a coloring agent (g), a thermosetting component (f), a curing accelerator (g), a filler (h) and a general-purpose additive (z). good too. For example, by using an energy ray-curable resin composition containing an energy ray-curable component (a) and a thermosetting component (f), the energy ray-curable resin layer (I) formed is exposed by heating. The adhesive force to the adherend 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)]
The photopolymerization initiator (c) includes, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin compounds such as benzoin dimethyl ketal; - Acetophenone compounds such as hydroxy-2-methyl-1-phenyl-propan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4,6-trimethylbenzoyl)phenyl acylphosphine oxide compounds such as phosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfide compounds such as benzylphenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexylphenyl ketone azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, Benzophenone compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); peroxide compounds; diketone compounds such as diacetyl benzyl; dibenzyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone; In addition, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines; and the like 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 0.5 parts per 100 parts by mass of the energy ray-curable compound (a). 01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, still more 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 ray The cured resin layer (I') obtained by curing the curable resin layer (I) has improved 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 group possessed by the energy ray-curable component (a), the polymer (b), etc., and is preferably a silane coupling agent. more preferred.
Silane coupling agents include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino ) propylmethyldiethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane , bis(3-triethoxysilylpropyl)tetrasulfane, methyltrimethoxysilane, 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, still more preferably 0.1 to 5 parts by mass. When the content of the coupling agent (d) is at least the above lower limit, effects such as improved dispersibility of the filler in the resin and improved adhesion of the energy ray-curable resin layer (I) can be obtained more remarkably. By being equal to or less than the above upper limit, outgassing is suppressed.

[Crosslinking agent (e)]
By cross-linking the energy ray-curable component (a), the polymer (b), etc. using the cross-linking agent (e), the initial adhesive strength and cohesive strength 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. is mentioned.

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

More specifically, the organic polyvalent isocyanate compound includes, for example, 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate; 4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; compounds in which one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate are added to all or part of the hydroxyl groups of polyols such as lysine diisocyanate;

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

When using an organic polyvalent isocyanate compound 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/or Alternatively, a crosslinked structure can be easily introduced into the energy ray-curable resin layer (I) by 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 based on a total of 100 parts by mass of the energy ray-curable component (a) and the polymer (b). , preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 0.5 to 5 parts by mass.

[Thermosetting component (f)]
The thermosetting component (f) includes, for example, epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc. Among these, epoxy thermosetting resins are preferred.
The thermosetting component (f) may be used alone or in combination of two or more.

(epoxy thermosetting resin)
The epoxy 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 resins, bisphenol A diglycidyl ether and hydrogenated products thereof, ortho-cresol novolak epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins. Bifunctional or higher epoxy compounds such as resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins can be used.
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), 2-propenyl group (allyl group), (meth)acryloyl group, (meth)acrylamide group, etc. is used. good too. 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 30000, more preferably 300 to 30000, more preferably 400 to 10,000, more preferably 500 to 3,000.
The epoxy equivalent of the epoxy resin (f1) is preferably 100-1000 g/eq, more preferably 150-800 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 carboxyl group, and an anhydrided group of an acid group. 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 thermosetting agents (f2), phenol-based curing agents having phenolic hydroxyl groups include, for example, polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
Among the thermosetting agents (f2), amine-based curing agents having an amino group include, for example, dicyandiamide.
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). Department.

[Curing accelerator (g)]
The curing accelerator (g) is a component for adjusting the curing speed 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; tributylphosphine, diphenylphosphine, triphenylphosphine, etc. organic phosphines; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate;
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, can be arbitrarily selected according to the purpose, and is not particularly limited. Examples include fillers, colorants, plasticizers, antistatic agents, antioxidants, gettering agents etc.
Each general-purpose additive (z) may be used alone or in combination of two or more.

Examples of fillers include inorganic fillers and organic fillers, and by using these, the thermal expansion coefficient of the cured resin layer (I') can be adjusted.
The energy ray-curable resin layer (I) may or may not contain a filler. From the viewpoint of suppression, it is preferably 5 to 87% by mass with respect to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). , more preferably 7 to 78% by mass.
Examples of fillers include those made of thermally conductive materials.
Examples of inorganic fillers include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, and boron nitride; beads obtained by spheroidizing these inorganic fillers; and surface-modified products of these inorganic fillers. single crystal fibers of these inorganic fillers; and glass fibers.
The average particle size of the filler is preferably 0.01-20 μm, more preferably 0.1-15 μm, still more preferably 0.3-10 μm. When the average particle size of the filler is within the above range, the decrease in transmittance of the energy ray-curable resin layer (I) can be suppressed while maintaining the adhesiveness of the cured resin layer (I′).

The energy ray-curable resin composition may or may not contain a coloring agent, but when it contains a coloring agent, the content is preferably as small as possible. , preferably less than 5% by mass, more preferably 0 less than 0.1 wt%, more preferably less than 0.01 wt%, even more preferably less than 0.001 wt%.

<<Method for producing energy ray-curable resin composition>>
An energy ray-curable resin composition is obtained by blending each component for constituting the composition.
There are no particular restrictions on the order of addition of each component when blending them, and two or more components may be added at the same time.
When using a solvent, it may be used by mixing the solvent with any of the ingredients other than the solvent and diluting this ingredient in advance, or by diluting any of the ingredients other than the solvent in advance. You may use by mixing a solvent with these compounding ingredients, without preserving.
The method of mixing each component at the time of blending is not particularly limited, and may be selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves. It can be selected as appropriate.
The temperature and time at which each component is added and mixed are not particularly limited as long as each compounded component is not deteriorated and may be adjusted as appropriate, but the temperature is preferably 15 to 30°C.

Examples of the solvent include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol) and 1-butanol; esters such as ethyl acetate; , ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. 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 more uniformly mixed. A solvent may be used independently and may use 2 or more types together.

The energy ray-curable resin layer (I) may have a single layer structure, or may have a multilayer structure of two or more layers.
As the energy ray-curable resin layer (I) composed of two or more layers, for example, an energy ray-curable resin layer (I- i) and an energy ray-curable resin layer (I-ii) having high adhesive strength. In the case of having such a configuration, by arranging the energy ray-curable resin layer (I-ii) on the surface on which the sealing target is placed, the sealing target can be firmly fixed and at the same time. After curing, the cured resin layer (I') obtained by curing the energy ray-curable resin layer (Ii) effectively suppresses warping, so that the performance as a temporary fixing layer and the warp prevention layer It is possible to achieve both performance as a higher level. Preferred compositions and physical properties of the energy ray-curable resin layers (Ii) and (I-ii) are selected from among the preferred compositions and physical properties of the energy ray-curable resin layer (I) described above, depending on the desired function. You just need to select the appropriate one and apply it.

The thickness of the energy ray-curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, even more preferably 10 to 200 μm, even more preferably 15 to 100 μm, and even 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, it is possible to obtain a cured encapsulant in which warping is more effectively suppressed. 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). The thickness of (I) means the total thickness of all layers constituting the energy ray-curable resin layer (I).

The storage elastic modulus E' of the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) at 23 ° C. From the viewpoint of making a laminate that can produce a stop body, the pressure 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 still more It is preferably 1.0×10 ⁹ or more, and is preferably 1.0×10 ¹³ Pa or less, more preferably 1.0×10 ¹² Pa or less, still more preferably 5.0×10 ¹¹ Pa or less, and more preferably 1.0×10 13 Pa or less. More preferably, it is 1.0×10 ¹¹ Pa or less.

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, and even more preferably 50% or more. is. Sufficient energy ray curability is obtained as visible light transmittance is the said range. Although there is no upper limit to the visible light transmittance, it can be, for example, 95% or less. The transmittance can be measured according to a known method using a spectrophotometer.

<Method for manufacturing laminate>
In the laminate of one embodiment of the present invention, for example, the pressure-sensitive adhesive layer (X), the base material (Y) and the energy ray-curable resin layer (I) are separately formed, and these are arranged so as to have a desired configuration. It can be manufactured by pasting together. Each layer can be formed, for example, by coating 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. As in the method of applying the resin composition (y) for forming and then applying the energy ray-curable resin composition thereon, the resin composition is applied sequentially on a specific layer to form a layer A method of forming and multilayering may be used. At that time, a plurality of layers may be applied simultaneously, for example, using a multi-layer coater or the like.

[Method for producing hardened sealing body]
A method for producing a cured sealant according to one embodiment of the present invention is a method for producing a cured sealant using the laminate according to one embodiment of the present invention, and includes the following steps (i) to (iv).
Step (i): A step of placing an object to be sealed on a portion 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 (iii) of forming a cured resin layer (I') by irradiating an energy ray to cure the energy ray-curable resin layer (I): the sealing object and the sealing object At least the surface of the cured resin layer (I') in the peripheral portion is coated with a thermosetting sealing material, and the sealing material is thermally cured to form a cured sealing body including the sealing object. Process step (iv): The cured resin layer (I′) and the support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles to obtain a cured sealant with a cured resin layer. Process Note that the cured sealing body in one aspect of the present invention is obtained by coating an object to be sealed with a sealing material and curing the sealing material. It is composed of a cured product.

FIG. 4 is a schematic cross-sectional view showing a process of manufacturing a cured sealing body using the laminate 1a shown in FIG. 1(a). Each of the above steps will be described below with reference to FIG. 4 as appropriate.

<Step (i)>
Step (i) is a step of placing an object to be sealed on part of the surface of the energy ray-curable resin layer (I) included in the laminate of one embodiment of the present invention.
In FIG. 4A, in this step, using the laminate 1a, the adhesive surface of the adhesive layer (X) of the support layer (II) is attached to the support 50, and the energy ray curable resin layer ( I) shows a state in which a sealing object 60 is placed on part of the surface.
Note that FIG. 4A shows an example using the layered product 1a shown in FIG. 1A; , the support, the laminate, and the object to be sealed are laminated or placed in this order.

As for the temperature conditions in step (i), it is preferable to perform the step (i) at a temperature at which the thermally expandable particles do not expand, for example, in an environment of 0 to 80°C (where the expansion start temperature (t) is 60 to 80°C). In some cases, it is preferably performed in an environment below the expansion start temperature (t).

The support is preferably attached to the entire adhesive surface of the adhesive layer (X) of the laminate.
Therefore, the support is preferably plate-like. Also, the area of the adhesive surface of the adhesive layer (X) and the surface of the support on the sticking side is preferably equal to or greater than the area of the adhesive surface of the adhesive layer (X), as shown in FIG.

Depending on the type of the object to be sealed, the type of sealing material used in step (ii), etc., the material that constitutes the support is selected as appropriate after considering the required properties such as mechanical strength and heat resistance. selected.
Specific materials constituting the support include, for example, metallic 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, polyimide resins, Resin materials such as polyamide-imide resins; composite materials such as glass epoxy resins; among these, SUS, glass, and silicon wafers are preferred. Moreover, from the viewpoint of enabling the energy ray-curable resin layer (I) to be irradiated with energy rays through the support, the support is preferably a transparent material such as glass.
Engineering plastics include nylon, polycarbonate (PC), and polyethylene terephthalate (PET).
Super engineering plastics include polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), and the like.

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

On the other hand, the sealing object placed on a part of the surface of the energy ray-curable resin layer (I) includes, for example, semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic parts, sapphire substrates, displays, Panel substrates and the like are included.

When the object to be sealed is a semiconductor chip, a semiconductor chip with a cured resin layer can be manufactured using the laminate of one embodiment of the present invention.
A conventionally known semiconductor chip can be used, and an integrated circuit composed of circuit elements such as transistors, resistors, and capacitors is formed on the circuit surface.
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, after the mounting, the circuit surface of the semiconductor chip is exposed.
A known device such as a flip chip bonder or a die bonder can be used for mounting the semiconductor chip.
The layout of arrangement of semiconductor chips, the number of arrangement, etc. may be appropriately determined according to the form of the intended package, the production volume, and the like.

Here, the laminated body of one embodiment of the present invention includes a semiconductor chip covered with a sealing material in a region larger than the chip size, such as FOWLP and FOPLP, so that not only the circuit surface of the semiconductor chip but also the sealing material is preferably applied to a package in which a rewiring layer is formed even in the surface region of
Therefore, the semiconductor chips are placed on a part of the surface of the energy ray-curable resin layer (I), and a plurality of semiconductor chips are arranged on the surface at regular intervals. It is preferable that a plurality of semiconductor chips are mounted on the surface, and more preferably, a 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 intended package.

<Step (ii)>
Step (ii) is a step of irradiating the energy ray-curable resin layer (I) with energy rays to cure the energy ray-curable resin layer (I) to form a cured resin layer (I'). be.
FIG. 4(b) shows a state in which the energy ray-curable resin layer (I) is cured in this step to form a cured resin layer (I').
The type of energy ray and irradiation conditions are not particularly limited as long as the type and conditions are such that the energy ray-curable resin layer (I) is cured to the extent that it sufficiently exhibits its function. It may be appropriately selected according to the process to be performed.
The illuminance of the energy ray during curing of the energy ray-curable resin layer (I) is preferably 4 to 280 mW/cm ² , and the light amount of the energy ray during curing is preferably 5 to 1000 mJ/cm ² . Preferably, 100 to 500 mJ/cm ² is more preferable.
The type of energy beam and the irradiation device are as described above.
The energy ray may be applied from any direction as long as the energy ray can be applied to the energy ray-curable resin layer (I). By using a material having an excellent An energy ray can be irradiated to the energy ray-curable resin layer (I) through the support 50, the pressure-sensitive adhesive layer (X) and the substrate (Y)).

<Step (iii)>
In the step (iii), the object to be sealed and the surface of the cured resin layer (I') at least in the periphery of the object to be sealed are coated with a thermosetting sealing material (hereinafter referred to as "coating treatment ”) is a step of thermally curing the sealing material to form a cured sealing body including the sealing object.
In the coating process, first, the object to be sealed and at least the periphery of the object to be sealed on the surface of the cured resin layer (I') are coated with the sealing material.
The sealing material also fills the gaps between the plurality of semiconductor chips while covering the entire exposed surface of the sealing object.
For example, FIG. 4(c) shows a state in which the sealing material 70 covers all the surfaces of the sealing object 60 and the cured resin layer (I').

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

As the coating method, it is possible to appropriately select and apply it according to the type of the sealing material from among the methods applied to the conventional sealing process. method, spin coating method, die coating method, transfer molding method, compression molding method and the like can be applied.

After the coating treatment, the sealing material is thermally cured to obtain a cured sealed body in which the sealing object is sealed with the sealing material.
The heat curing treatment in step (iii) is performed at a temperature at which the thermally expandable particles do not expand. It is preferably carried out under temperature conditions below the temperature (t).

In the manufacturing method of one aspect of the present invention, as shown in FIG. Heat curing is performed in this state.
Since the cured resin layer (I') is provided, the difference in shrinkage stress between the two surfaces of the resulting cured sealant can be reduced, and warpage occurring in the cured sealant can be effectively suppressed. Conceivable.

<Step (iv)>
In the step (iv), the cured resin layer (I′) and the support layer (II) are separated at their interface by the treatment of expanding the thermally expandable particles to obtain a cured sealing body with the cured resin layer. It is a process.
FIG. 4(d) shows a state in which the cured resin layer (I') and the support layer (II) are separated at the interface P by the treatment for expanding the thermally expandable particles.
As shown in FIG. 4( d ), by separating at the interface P, a cured resin layer having a cured sealing body 80 in which the sealing object 60 is sealed and a cured resin layer (I′). A cured sealing body 100 can be obtained.
The presence of the cured resin layer (I') has the function of effectively suppressing the warpage that occurs in the cured sealing body, protects the sealing target, and improves the reliability of the sealing target. contribute.

The "expansion treatment" in step (iv) is a treatment for expanding the thermally expandable particles by heating them at an expansion start temperature (t) or higher, and the cured resin layer (I ') surface of the supporting layer (II) becomes uneven. As a result, they can be easily separated collectively at the interface P with a slight force.
The "expansion start temperature (t) or higher temperature" when expanding the thermally expandable particles is preferably "expansion start temperature (t) + 10°C" or higher and "expansion start temperature (t) + 60°C" or lower. , "expansion start temperature (t) + 15°C" or higher and "expansion start temperature (t) + 40°C" or lower.
The heating method is not particularly limited, and examples thereof include a heating method using a hot plate, an oven, a kiln, an infrared lamp, a hot air blower, etc. However, the heating method between the support layer (II) and the cured resin layer (I') is From the viewpoint of facilitating separation at the interface P, a method in which a heat source for heating can be provided on the support 50 side is preferable.

The cured sealing body with the cured resin layer obtained in this way is then subjected to further necessary processing. An example is described below. In addition, in the following description, a mode in which a semiconductor chip 60 is used as the sealing object 60 will be described.

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

<Rewiring Layer and External Terminal Electrode Forming Process>
FIG. 5(c) shows a rewiring layer 200 and an external terminal electrode 300 which 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. Wiring layers 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 if necessary, one or more insulating layers may be provided.
The external terminal electrodes 300 are electrically connected to external electrode pads of the rewiring layer 200 . The external electronic electrodes 300 can be formed, for example, by soldering solder balls or the like.

<Dicing process>
FIG. 5D shows a step of dicing the cured sealing body 100 with the cured resin layer to which the external terminal electrodes 300 are connected.
Dicing may be performed for each semiconductor chip, or may be performed for a predetermined size including a plurality of semiconductor chips. A method for dicing the cured sealing body 100 with the cured resin layer is not particularly limited, and the dicing can be performed by a cutting means such as a dicing saw.

<Second Grinding Process>
FIG. 5(e) shows a second grinding step in which the cured resin layer (I') disposed on the opposite side of the rewiring layer 200 of the cured sealing body 80 is ground by the grinding means 110. ing. At this time, the surface of the cured sealant 80 on the side of the rewiring layer 200 is preferably fixed with a back grind tape or the like. Grinding means 110 includes the same means as in the first grinding step.
In the second grinding step, 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 resulting 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 part of the cured resin layer (I') is ground, the cured resin layer (I') also serves to protect the back surface of the semiconductor chip 60. be able to.

The present embodiment will be specifically described by 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".
Further, the physical property values in each example are values measured by the following methods.

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

<Measurement of thickness of each layer>
It was measured using a constant-pressure thickness measuring instrument manufactured by Teclock Co., Ltd. (model number: “PG-02J”, standard specifications: 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.
An aluminum cup with a diameter of 6.0 mm (inner diameter of 5.65 mm) and a depth of 4.8 mm was filled with 0.5 mg of thermally expandable particles to be measured, and an aluminum lid (5.6 mm in diameter and 0.6 mm in thickness) was placed thereon. 1 mm) is placed on the sample.
Using a dynamic viscoelasticity measuring device, the height of the sample is measured while a force of 0.01 N is applied to the sample from the top of the aluminum lid with a pressurizer. Then, while applying a force of 0.01 N by the pressurizer, heat is applied from 20° C. to 300° C. at a temperature increase rate of 10° C./min, and the amount of displacement in the vertical direction of the pressurizer is measured. Let the displacement start temperature be the expansion start temperature (t).
The maximum expansion temperature was defined as the temperature at which the amount of displacement measured by the above method was maximized.

<Evaluation of warpage>
The curable resin layer (I) of the sheet for forming the curable resin layer (I) 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 curable resin layer (I)/silicon wafer/thermosetting resin composition layer in this order was obtained.
Subsequently, when the curable resin layer (I) is the energy ray curable resin layer (I), ultraviolet rays are applied at an illuminance of 215 mW/cm ² using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Corporation). , and a light amount of 187 mJ/cm ² for three times to cure the energy ray-curable resin layer (I) to form a cured resin layer (I′). When the curable resin layer (I) was the thermosetting resin layer (I), it was cured by heating at 180° C. for 60 minutes to form a cured resin layer (I′). After that, the thermosetting resin composition is heated and cured to form a thermosetting resin layer, and a cured measurement sample having a cured resin layer (I′)/silicon wafer/thermosetting resin layer in this order is obtained. Obtained.
After the cured measurement sample was placed on a horizontal table, it was visually observed, and the presence or absence of warping was evaluated based on the following criteria. The "silicon wafer/thermosetting resin layer" portion of the measurement sample after curing corresponds to a cured sealing body obtained by sealing a semiconductor chip with a thermosetting resin. The performance of the layer (I') as an anti-warpage layer can be evaluated.
A: The amount of warpage is 3 mm or less.
B: The amount of warpage is greater than 3 mm and less than 15 mm.
C: The amount of warp is 15 mm or more.
The amount of warp was 15 mm when the silicon wafer/thermosetting resin layer was formed in the same procedure as above without adhering the curable resin layer (I).

<Evaluation of Separability>
After attaching a silicon wafer to the surface of the curable resin layer (I) of the laminate obtained in each example, the curable resin layer (I) is cured by energy rays or heat to form a cured resin layer (I'). formed. Next, by expanding the expandable base layer (Y1) by thermal expansion treatment, the cured resin layer (I') and the support layer (II) are separated, and the separability is evaluated based on the following criteria. did. 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 the conditions described in Examples 1 to 5 and Reference Example 1 described later. .
A: Separable, the appearance of the cured resin layer (I') is good, and there is no adhesive residue.
B: Separable and the appearance of the cured resin layer (I′) is good, but there is some adhesive residue.
C: The cured resin layer (I') cannot be separated, or there is adhesive residue on the entire surface of the cured resin layer (I'), or the appearance of the cured resin layer (I') is unsatisfactory.

<Storage Elastic Modulus E′ of Expandable Base Layer (Y1)>
A 200 μm thick expandable substrate layer (Y1) prepared for storage modulus E′ measurement was made into a size of 5 mm long×30 mm wide×200 μm thick, and the release material was removed to prepare 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 increase 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 was measured at a predetermined temperature 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 circles with a diameter of 8 mm, the release material was removed, and the thickness was 3 mm. .
Using a viscoelasticity measuring device (manufactured by Anton Paar, device name "MCR300"), the torsional shear method was performed under the conditions of a test start temperature of 0 ° C., a test end temperature of 300 ° C., a temperature increase rate of 3 ° C./min, and a frequency of 1 Hz. measured the storage shear modulus G' of the test samples at a given temperature.

<Storage elastic modulus E' of cured resin layer (I')>
Using a test piece obtained by curing the curable resin layer (I) obtained in each example, using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), the test start temperature The storage elastic modulus E' of the formed cured resin layer (I') was measured at 23°C under 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. In addition, when the curable resin layer (I) is the energy ray curable resin layer (I), the test piece is irradiated with ultraviolet rays using an ultraviolet irradiation device RAD-2000 (manufactured by Lintec Corporation) at an illuminance of 215 mW. /cm ² and a light intensity of 187 mJ/cm ² , and when the curable resin layer (I) is the thermosetting resin layer (I), the material is heated at 180° C. for 60 minutes. and hardened.

Synthesis example 1
(Synthesis of "acrylic urethane resin" used for expandable substrate layer (Y1))
In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate was added to 100 parts by mass of a polycarbonate diol (carbonate type diol) having a mass average molecular weight of 1,000 so that the equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of the isophorone diisocyanate was 1. Then, 160 parts by mass of toluene was added, and the mixture was reacted at 80° C. for 6 hours or more under a nitrogen atmosphere with stirring 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. A urethane prepolymer having an average molecular weight of 29,000 was obtained.
Subsequently, in a reaction vessel under a nitrogen atmosphere, 100 parts by mass of the urethane prepolymer obtained above, 117 parts by mass of methyl methacrylate (MMA), 5.1 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA), 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. while stirring. Then, in the reaction vessel, a solution obtained by further diluting 2.2 parts by mass of a 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. dripped over.
After completion of the dropwise addition, the mixture was allowed to react 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 sheet for forming support layer (II)]
Production example 1
(Support layer (II-A))
A support layer (II-A) forming sheet was produced according to the following procedures (1-1) to (1-4).
The details of the materials used to form each layer are as follows.

<Adhesive resin>
-Acrylic copolymer (i): 2-ethylhexyl acrylate (2EHA) / 2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) having structural units derived from raw material monomers, Mw 600,000 acrylic copolymer.
- Acrylic copolymer (ii): n-butyl acrylate (BA)/methyl methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid = 86.0/8.0/5.0/1. 0 (mass ratio) acrylic copolymer having Mw of 600,000 and having constituent units derived from raw material monomers.
<Additive>
· Isocyanate cross-linking agent (i): manufactured by Tosoh Corporation, product name "Coronate L", solid content concentration: 75% by mass.
<Thermal expandable particles>
- Thermally expandable particles A: Kureha Co., Ltd., product name "S2640", expansion start temperature (t) = 208°C, average particle size ( _D50 ) = 24 µm, ₉₀ % particle size (D90) = 49 µm.
<Release material>
· Heavy release film: manufactured by Lintec Corporation, product name "SP-PET382150", a polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 µm.
· Light release film: product name “SP-PET381031” manufactured by Lintec Corporation, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm.

(1-1) Formation of the first pressure-sensitive adhesive layer (X1) To 100 parts by mass of the solid content of the acrylic copolymer (i), which is an adhesive resin, 5.0 parts by mass of the isocyanate-based cross-linking agent (i) The parts were blended, diluted with toluene, and uniformly stirred 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 "release-treated surface") to form a coating film, and the coating film is dried at 100 ° C. for 60 seconds. Thus, a first pressure-sensitive adhesive layer (X1), which is a non-thermally expandable pressure-sensitive adhesive layer with a thickness of 5 μm, was formed.
The storage shear modulus G'(23) of the first pressure-sensitive adhesive layer (X1) at 23°C was 2.5 × 10 ⁵ Pa.
In addition, 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 the second pressure-sensitive adhesive layer (X2) In 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 blended, diluted with toluene, and uniformly stirred to prepare a pressure-sensitive adhesive composition having a solid content concentration (active ingredient concentration) of 25% by mass.
Then, the adhesive composition is applied to the release-treated surface of the light release film to form a coating film, the coating film is dried at 100 ° C. for 60 seconds, and a second adhesive layer having a thickness of 10 μm ( X2) was formed.
The storage shear modulus G'(23) of the second pressure-sensitive adhesive layer (X2) at 23°C was 9.0 x ^104Pa .
In addition, 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), and dioctyltinbis as a catalyst. 1.4 parts by mass of (2-ethylhexanoate) and the above thermally expandable particles A are blended, diluted with toluene, and uniformly stirred to form a resin composition having a solid content concentration (active ingredient concentration) of 30% by mass. prepared the product.
The content of the thermally expandable particles A was 20% by mass with respect to the total amount (100% by mass) of the active ingredients in the resulting resin composition.
Then, on the surface of a 50 μm thick polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name “Cosmoshine A4100”, probe tack value: 0 mN / 5 mmφ), which is a non-expanding substrate, the resin composition A material was applied to form a coating film, and the coating film was dried at 100° C. for 120 seconds to form an expandable substrate layer (Y1) having a thickness of 50 μm.
Here, the PET film, which is the non-expanding substrate, corresponds to the non-expanding substrate layer (Y2).
As described above, a substrate (Y) composed of an expandable substrate layer (Y1) having a thickness of 50 μm and a non-expanding substrate layer (Y2) having a thickness of 50 μm was produced.

As a sample for measuring the storage elastic modulus E′ and probe tack value of the expandable substrate layer (Y1), the resin composition was applied to the release-treated surface of the light release film to form a coating film, The coating film was dried at an ambient temperature of 100° C. for 120 seconds to form an expandable substrate layer (Y1) having a thickness of 200 μm in the same manner.
Then, the storage elastic modulus and probe tack value at each temperature of the expandable substrate layer (Y1) were measured based on the above-described measurement method. The measurement results were as follows.
・Storage modulus E′(23) at 23° C.=2.0×10 ⁸ Pa
・Storage modulus E′(100) at 100° C.=3.0×10 ⁶ Pa
・Storage modulus E′(208) at 208° C.=5.0×10 ⁵ Pa
・Probe tack value = 0mN/5mmφ

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

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

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

In Production Examples 2 and 3, when forming the sheet for forming the support layer (II), the drying temperature after coating the resin composition to form the coating film was the expansion start temperature of the thermally expandable particles ( Although the drying temperature is higher than t), no bubbles were observed in the formed support layer (II) because the drying temperature was the ambient temperature.

Production example 4
(Support layer (II-D))
In Production Example 1, the thermally expandable particles A were changed to the following thermally expandable particles D, and the drying conditions after coating the resin composition to form a coating film were changed to an ambient temperature of 100° C. for 1 minute. A support layer (II-D) forming sheet was produced in the same manner as in Production Example 1 except for the above.
- Thermally expandable particles D: manufactured by Nippon Philite 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))
A curable composition with a solid content concentration (active ingredient concentration) of 61% by mass by blending each component of the type and amount shown below (both "active ingredient ratio"), further diluted with methyl ethyl ketone, and stirred uniformly. A solution of the product was prepared.
[(a2) component]
・ Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name “KAYARAD DPHA”): 17.6 parts by mass [component (b)]
- Acrylic polymer: butyl acrylate (BA) (55 parts by mass), methyl acrylate (MA) (10 parts by mass), glycidyl methacrylate (GMA) (20 parts by mass) and 2-hydroxyethyl acrylate ( Acrylic resin (glass transition temperature: −28° C., Mw: 800,000) obtained by copolymerizing HEA) (15 parts by mass): 17 parts by mass [component (c)]
Phenyl 1-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 [component (f)]
・ Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name “BPA328”): 16 parts by mass ・ Dicyclopentadiene type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name “XD-1000L”): 18 parts by mass・Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, product name “HP-7200HH”): 27 parts by mass ・Dicyandiamide (manufactured by ADEKA Corporation, product name “ADEKA DONOR 3636AS”): 1.5 parts by mass [( g) component]
- Imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., product name "2PH-Z"): 1.5 parts by mass

The solution of the curable composition prepared above is applied on the release-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 beam with a thickness of 25 μm. A curable resin layer (IA) was formed, and a sheet for forming an energy ray curable resin layer (IA) comprising the energy ray curable resin layer (IA) and a light release film was produced.

Production example 6
(Energy ray-curable resin layer (IB))
A curable composition with a solid content concentration (active ingredient concentration) of 61% by mass by blending each component of the type and amount shown below (both "active ingredient ratio"), further diluted with methyl ethyl ketone, and stirred uniformly. A solution of the product was prepared.
[(a2) component]
- ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical 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 [component (c) ]
· 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone (manufactured by BASF, product name "Irgacure (registered trademark) 369"): 0.6 parts by mass [(d) component]
3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-503”): 0.4 parts by mass [(h) component]
・Silica filler (fused silica filler, average particle size 8 μm): 57 parts by mass [component (z)]
32 parts by weight of a phthalocyanine blue pigment (Pigment Blue 15:3), 18 parts by weight of an isoindolinone yellow pigment (Pigment Yellow 139), and 50 parts by weight of an anthraquinone red pigment (Pigment Red 177) are mixed, Pigment obtained by pigmenting such that the total amount of the above three 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 on the release-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 beam with a thickness of 25 μm. A curable resin layer (IB) was formed, and a sheet for forming an energy ray curable resin layer (IB) comprising the energy ray curable resin layer (IB) and a light release film was produced.

Production example 7
(Thermosetting resin layer (IC))
Each component of the type and amount shown below (both "active ingredient ratio") is blended, further diluted with methylethiketone, stirred uniformly, and cured to a solid content concentration (active ingredient concentration) of 61% by mass. A solution of the sexual composition was prepared.
- Acrylic polymer: butyl acrylate (BA) (1 part by mass), methyl acrylate (MA) (74 parts by mass), glycidyl methacrylate (GMA) (15 parts by mass) and 2-hydroxyethyl acrylate ( HEA) (10 parts by mass) acrylic resin (glass transition temperature: 8 ° C., Mw: 440,000): 18 parts by mass Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name "BPA328"): 3 parts by mass Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "Epicoat 1055"): 20 parts by mass Dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "XD-1000L"): 1.5 parts by mass Dicyandiamide (manufactured by ADEKA, product name "Adekaber 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 Corporation, product name “MSEP2”): 0.5 parts by mass ・Spherical silica filler (manufactured by Admatechs 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 on the release-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 heat harden to a thickness of 25 μm. A thermosetting resin layer (IC) was formed, and a sheet for forming a thermosetting resin layer (IC) composed of the thermosetting resin layer (IC) and a light release film was produced.

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

[Preparation of cured sealing body]
Subsequently, using the laminate obtained in each example, a cured sealing body was produced according to the following procedure.

(1) Placement of semiconductor chip Remove the light release film on the support layer (II) side of the laminate, and place the exposed adhesive surface of the second adhesive layer (X2) of the support layer (II) on the support ( glass).
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 x 6.4 mm) were placed on the exposed surface of the curable resin layer (I). 4 mm and a chip thickness of 200 μm (#2000)) were 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 Cured Resin Layer (I′) In Examples 1 to 5, after the above (1) and before the following (3), an energy ray-curable resin layer that is the curable resin layer (I) (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 under the conditions of an illuminance of 215 mW/cm ² and a light amount of 187 mJ/cm ² using an ultraviolet irradiation apparatus RAD-2000 (manufactured by Lintec Corporation).
In Reference Example 1, (2) was not performed, and the thermosetting resin layer, which was the curable resin layer (I), was cured at the same time as the sealing material was cured in (3) described later.

(3) Formation of cured encapsulant The nine semiconductor chips and the surface of the cured resin layer (I') (the thermosetting resin layer in Reference Example 1) at least around the semiconductor chips were sealed. It is covered with a thermosetting sealing resin film that is a sealing material, and a vacuum heating and pressurizing laminator (manufactured by ROHM and HAAS, product name “7024HP5”) is used to heat and cure the sealing resin film. A stop body was produced. In addition, 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 for 3 minutes at a temperature of the expansion start temperature (t) of the thermally expandable particles contained in the support layer (II) of each laminate + 30 ° C. and separated at the interface P between the first pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I'). Thus, a cured sealing body with a cured resin layer was obtained.

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

1a, 1b, 2a, 2b, 3 Laminate (I) Energy ray-curable resin layer (I') Cured resin layer (II) Support layer (X) Adhesive layer (X1) First adhesive layer (X2) 2 adhesive layer (Y) substrate (Y1) expandable substrate layer (Y2) non-expandable substrate layer 50 support 60 sealing object (semiconductor chip)
70 sealing material 80 cured sealing body 100 cured sealing body with cured resin layer 100a cured sealing body surface 110 grinding means 200 rewiring layer 300 external terminal electrode

Claims (11)

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 a sticky surface,
The support layer (II) has a substrate (Y) and an adhesive layer (X), at least one of the substrate (Y) and the adhesive layer (X) contains thermally expandable particles,
A laminate in which a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) and a support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles. The cured resin layer (I′) obtained by curing the energy ray-curable resin layer (I) has a storage elastic modulus E′ at 23° C. of 1.0×10 ⁷ to 1.0×10 ¹³ Pa. Item 1. The laminate according to item 1. 3. The laminate according to claim 1, wherein the energy ray-curable resin layer (I) has a thickness of 1 to 500 μm. 4. 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 substrate (Y) has an expandable substrate layer (Y1) containing the thermally expandable particles. 6. The laminate according to claim 5, wherein the pressure-sensitive adhesive layer (X) is a non-expanding pressure-sensitive adhesive layer. 7. 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 substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1),
The support layer (II) has a non-expandable base layer (Y2), an expandable base layer (Y1), and an adhesive layer (X) in this order,
8. The laminate according to any one of claims 5 to 7, wherein the adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated. placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I),
irradiating the energy ray-curable resin layer (I) with an energy ray to form a cured resin layer (I') by curing the energy ray-curable resin layer (I);
covering the object to be sealed and the surface of the cured resin layer (I′) at least in the periphery of the object to be sealed with a thermosetting sealing material;
After the sealing material is thermally cured, the cured resin layer (I′) and the support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles, and the sealing object is separated. Laminate according to any one of claims 1 to 8, which is used to form a cured encapsulant comprising. 10. The laminate according to claim 9, which is used to prevent warping of the hardened encapsulant. A method for producing a cured sealant using the laminate according to any one of claims 1 to 10, comprising the following steps (i) to (iv).
Step (i): A step of placing an object to be sealed on a portion 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 (iii) of forming a cured resin layer (I') by irradiating an energy ray to cure the energy ray-curable resin layer (I): the sealing object and the sealing object At least the surface of the cured resin layer (I') in the peripheral portion is coated with a thermosetting sealing material, and the sealing material is thermally cured to form a cured sealing body including the sealing object. Process step (iv): The cured resin layer (I′) and the support layer (II) are separated at their interface by a treatment for expanding the thermally expandable particles to obtain a cured sealant with a cured resin layer. process

Images