CN112789334A

CN112789334A - Laminate and method for producing cured sealing body

Info

Publication number: CN112789334A
Application number: CN201880098044.9A
Authority: CN
Inventors: 佐藤明德; 高丽洋佑; 阿久津高志; 垣内康彦; 冈本直也; 山田忠知; 中山武人
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2018-10-02
Filing date: 2018-10-02
Publication date: 2021-05-11
Anticipated expiration: 2038-10-02
Also published as: CN112789334B; KR20210044836A; KR102543787B1; WO2020070790A1; JP7129110B2; JPWO2020070790A1

Abstract

The present invention relates to a laminate comprising an energy ray-curable resin layer (I) and a support layer (II) supporting the energy ray-curable resin layer (I), wherein the energy ray-curable resin layer (I) has an adhesive surface, the support layer (II) comprises a base material (Y) and an adhesive layer, at least one of the base material (Y) and the adhesive layer contains thermally expandable particles, and a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) and the support layer (II) are separated at the interface thereof by a treatment of expanding the thermally expandable particles.

Description

Laminate and method for producing cured sealing body

Technical Field

The present invention relates to a method for producing a laminate and a cured sealing body.

Background

In recent years, electronic devices have been made smaller, lighter, and more functional, and semiconductor chips are sometimes mounted in packages having dimensions close to those of the electronic devices. Such a Package is sometimes called a CSP (Chip Scale Package). The CSP includes: wafer Level Package (WLP) in which a Package is completed by performing a process up to a final packaging process at a Wafer size, Panel Level Package (PLP) in which a Package is completed by performing a process up to a final packaging process at a Panel size larger than a Wafer size, and the like.

WLP and PLP are classified into Fan-In (Fan-In) type and Fan-Out (Fan-Out) type. In fan-out WLP (hereinafter also referred to as "FOWLP") and PLP (hereinafter also referred to as "FOPLP"), a semiconductor chip is covered with a sealing material to form a region larger than the chip size, and a re-wiring layer and an external electrode are formed not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material to form a cured sealing body of the semiconductor chip.

FOWLP and FOPLP can be manufactured, for example, by the following steps: a mounting step of mounting a plurality of semiconductor chips on the temporary fixing sheet; a coating step of coating the substrate with a thermosetting sealing material; a curing step of obtaining a cured sealing body by thermally curing the sealing material; a separation step of separating the cured sealing body from the temporary fixing sheet; and a rewiring layer forming step of forming a rewiring layer on the exposed surface of the semiconductor chip side (hereinafter, the processing performed in the coating step and the curing step is also referred to as "sealing processing").

Patent document 1 discloses a heat-peelable pressure-sensitive adhesive sheet for temporary fixation when an electronic component is cut, which comprises a substrate and a heat-expandable pressure-sensitive adhesive layer provided on at least one surface of the substrate and containing heat-expandable microspheres. In the production of FOWLP and FOPLP, it is also conceivable to use the heat-peelable pressure-sensitive adhesive sheet described in patent document 1.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 3594853

Disclosure of Invention

Problems to be solved by the invention

However, if the cured seal is produced using the adhesive sheet described in patent document 1 as a temporary fixing sheet, the cured seal tends to warp due to heat shrinkage. This is believed to be due to: since the semiconductor chips sealed in the cured sealing body are collectively present on the one surface side in contact with the temporary fixing sheet, a region on the side where the proportion of the semiconductor chips having a small thermal expansion coefficient is relatively high and a region on the side where the proportion of the cured resin having a large thermal expansion coefficient is relatively high are generated in the cured sealing body, and stress is generated due to the difference in thermal shrinkage rate between the two regions. And this problem tends to become significant as the package size of FOWLP, FOPLP, or the like increases.

In the case of a cured sealing body having a warp, for example, when the cured sealing body is ground in a subsequent step, there is a possibility that a crack is likely to occur, and a trouble is likely to occur when the cured sealing body is transferred by a cantilever when the cured sealing body is transported by a device.

As a method for suppressing the warpage of the cured sealing body, for example, a method using a laminate including a temporary fixing layer provided with a thermally-expansible adhesive layer containing thermally-expansible particles and a thermosetting resin layer is conceivable. Namely the following method: and a method of performing the step of mounting the semiconductor chip on the thermosetting resin layer and the step of coating the semiconductor chip, then thermally curing the thermosetting resin layer and the sealing material to obtain a cured sealing body with a cured resin layer, and then foaming the thermally expandable particles to separate the cured sealing body with the cured resin layer from the temporary fixing layer. In this method, the cured resin layer functions as a warpage-preventing layer of the cured sealing body, and therefore, a cured sealing body in which the occurrence of warpage is suppressed can be obtained.

On the other hand, when the above method is used, since both the treatment for foaming the thermally expandable particles and the treatment for curing the thermosetting resin layer are heat treatments, the thermally expandable particles in the temporary fixing layer may be foamed in the heat treatment for curing the thermosetting resin layer. The present inventors have studied and found that 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.

Therefore, a laminate which can provide a cured sealing body with a cured resin layer as a warpage-preventing layer and can also be used for the production of a cured sealing body, and which can easily separate the cured resin layer from the temporary securing layer after the cured sealing body with the cured resin layer is formed, has been desired.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate including a support layer and a curable resin layer, which can be sealed by fixing an object to be sealed to the surface of the curable resin layer, can be provided with a cured resin layer as a warpage preventing layer for the cured seal formed by the sealing, and can be easily separated from the support layer, and a method for manufacturing a cured seal using the laminate.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following invention, and have completed the present invention.

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

[1] A laminate, comprising:

an energy ray-curable resin layer (I), and

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

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

the support layer (II) has a base material (Y) and an adhesive layer (X), at least one of the base material (Y) and the adhesive layer (X) containing thermally expandable particles,

the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) and the support layer (II) are separated at the interface by the treatment of expanding the thermally expandable particles.

[2]Above-mentioned [1]The laminate is characterized in that the cured resin layer (I ') obtained by curing the energy ray-curable resin layer (I) has a storage modulus E' of 1.0X 10 at 23 DEG C⁷～1.0×10¹³Pa。

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

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

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

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

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

[8] The laminate according to any one of [5] to [7], wherein,

the base material (Y) comprises a non-expandable base material layer (Y2) and an expandable base material layer (Y1),

the support layer (II) comprises a non-expandable base material layer (Y2), an expandable base material layer (Y1) and an adhesive layer (X) in this order,

the adhesive layer (X) and the energy ray-curable resin layer (I) are directly laminated together.

[9] The laminate according to any one of [1] to [8] above, which is used for forming a cured sealing body containing a sealing object as follows:

placing a sealing object 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') obtained by curing the energy ray-curable resin layer (I),

coating the object to be sealed and the surface of the cured resin layer (I') on at least the peripheral portion 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 the interface by the treatment of expanding the thermally expandable particles, thereby forming a cured sealing body including the object to be sealed.

[10] The laminate according to [9], which is used for preventing warpage of the cured sealing body.

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

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

step (ii): a step of irradiating the energy ray-curable resin layer (I) with an energy ray to form a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I)

Step (iii): a step of forming a cured sealing body including the object to be sealed by coating the object to be sealed and the surface of the cured resin layer (I') on at least the peripheral portion of the object to be sealed with a thermosetting sealing material and thermally curing the sealing material;

step (iv): and a step of separating the cured resin layer (I') from the support layer (II) at the interface thereof by the treatment of expanding the thermally expandable particles to obtain a cured sealing body with a cured resin layer.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a laminate having a support layer and a curable resin layer, which can be sealed by fixing an object to be sealed to the surface of the curable resin layer, can be provided with a cured resin layer as a warpage preventing layer for the cured seal formed by the sealing, and can be easily separated from the support layer, and a method for producing a cured seal using the laminate.

Drawings

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

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

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

Fig. 4 is a schematic cross-sectional view showing a step of producing a cured sealing body with a cured resin layer by using the laminate 1a shown in fig. 1 (a).

FIG. 5 is a schematic sectional view showing a method of processing a cured sealing body.

Description of the symbols

1a, 1b, 2a, 2b, 3 laminate

(I) Energy ray-curable resin layer

(I') curing the resin layer

(II) supporting layer

(X) adhesive layer

(X1) adhesive layer No. 1

(X2) 2 nd adhesive layer

(Y) base Material

(Y1) expandable base Material layer

(Y2) non-expandable substrate layer

50 support

60 object to be sealed (semiconductor chip)

70 sealing Material

80 cured seal

100 cured sealing body with cured resin layer

100a cured sealing body surface

110 grinding mechanism

200 rewiring layer

300 external terminal electrode

Detailed Description

In the present specification, whether or not the layer to be evaluated is a "non-expandable layer" can be determined as follows: after the treatment for swelling was performed for 3 minutes, when the volume change rate before and after the treatment was less than 5% as calculated from the following equation, the layer was determined to be a "non-swelling layer". On the other hand, when the volume change rate is 5% or more, the layer is determined to be an "expandable layer".

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

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

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

In the present specification, the weight average molecular weight (Mw) is a value in terms of standard polystyrene measured by a Gel Permeation Chromatography (GPC) method, specifically a value measured by the method described in examples.

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

In the present specification, regarding a preferable numerical range (for example, a range of contents), the lower limit value and the upper limit value described in sections may be independently combined. For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" may be combined to obtain "10 to 60".

In the present specification, unless otherwise specified, one kind of each of the exemplified components and materials may be used alone, or two or more kinds may be used in combination, and when two or more kinds are used in combination, the combination and ratio thereof may be arbitrarily selected.

In the present specification, the "energy ray" means a ray having an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation, an electron beam, and the like. The ultraviolet rays can be irradiated 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 may irradiate an electron beam generated by an electron beam accelerator or the like.

In the present specification, "energy ray-curable property" means a property that curing occurs by irradiation with an energy ray, and "non-energy ray-curable property" means a property that curing does not occur even if irradiation with an energy ray.

[ laminate ]

The laminate according to one embodiment of the present invention includes an energy ray-curable resin layer (I) and a support layer (II) that supports the energy ray-curable resin layer (I).

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

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

In the laminate according to one embodiment of the present invention, the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) and the support layer (II) may be separated at the interface thereof by a treatment of expanding the heat-expandable particles in the support layer (II). That is, in the laminate of one embodiment of the present invention, the thermal expansion particles expand by the thermal expansion treatment, and irregularities are generated on the surface of the layer containing the thermal expansion particles, so that the contact area between the support layer (II) and the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) decreases. As a result, the separation can be easily performed at a time with a small force at the interface between the support layer (II) and the cured resin layer (I').

In the laminate according to one embodiment of the present invention, since heating is not required when curing the energy ray-curable resin layer (I), the thermal expansion particles in the support layer (II) do not expand when curing the energy ray-curable resin layer (I), and a laminate excellent in separability between the support layer (II) and the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) can be formed.

A laminate according to an embodiment of the present invention is used for forming a cured sealing body including an object to be sealed as follows: the method for producing the cured sealing body includes the steps of placing a sealing object on a part of the surface of an 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 ') obtained by curing the energy ray-curable resin layer (I), coating the sealing object and the surface of the cured resin layer (I ') on at least the peripheral portion of the sealing object with a thermosetting sealing material, thermally curing the sealing material, and then separating the cured resin layer (I ') and a support layer (II) at the interface thereof by a process of expanding the thermally expandable particles to form the cured sealing body including the sealing object.

The cured sealing body formed by the above-described method is provided with the cured resin layer (I') on the side where the existence ratio of the semiconductor chip is relatively high. As a result, the difference in shrinkage stress between the two surfaces of the cured sealing body can be reduced, and the cured sealing body in which warpage is effectively suppressed can be obtained.

That is, the laminate according to one embodiment of the present invention is useful as a warpage prevention laminate for preventing a cured sealing body.

In this case, since the laminate according to one embodiment of the present invention has the energy ray-curable resin layer (I) in which the adhesive force can be easily adjusted to be higher than that of the thermosetting resin layer, the object to be sealed can be more reliably fixed to a part of the surface. In addition, when the thermosetting resin layer is heated at a high temperature, it is mainly softened at the initial stage of curing, and therefore, there is a possibility that chip misalignment may occur, whereas the energy ray-curable adhesive composition is not softened during curing by energy ray irradiation, and therefore, it is possible to avoid chip misalignment accompanying curing.

< construction of laminated body >

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

Fig. 1 to 3 are schematic cross-sectional views of laminates, showing the structures of the laminates according to the first to third embodiments of the present invention. In the laminate of the first to third embodiments of the present invention described below, the release material may be further laminated on the adhesive surface (i.e., the surface on the opposite side from the support) of the pressure-sensitive adhesive layer (X) (or the 2 nd pressure-sensitive adhesive layer (X2)) to be bonded to the support and the surface on the opposite side from the support layer (II) of the energy ray-curable resin layer (I).

[ laminate of first embodiment ]

As the laminate according to the first embodiment of the present invention,

laminates

1a and 1b shown in fig. 1 can be exemplified.

The

laminates

1a and 1b each include an energy ray-curable resin layer (I) and a support layer (II) having a substrate (Y) and an adhesive layer (X), and are configured such that the substrate (Y) and the energy ray-curable resin layer (I) are directly laminated together.

In the laminate according to the first embodiment of the present invention, the adhesive surface of the adhesive layer (X) is bonded to a support (not shown).

The support layer (II) is a layer containing thermally expandable particles in at least one layer, and in the laminate 1a, the base material (Y) is a single-layer base material composed only of an expandable base material layer (Y1) containing thermally expandable particles.

The substrate (Y) may be a single-layer structure substrate composed only of an expandable substrate layer (Y1) such as the laminate 1a shown in fig. 1(a), or may be a multilayer structure substrate having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2) such as the laminate 1b shown in fig. 1 (b). When the substrate (Y) includes the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2), the substrate (Y) may be composed of only the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2).

Preferably, 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 thermally expandable particles contained in the expandable base material layer (Y1) expand by the thermal expansion treatment, and irregularities are generated on the surface of the base material (Y), and the contact area with the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) in advance decreases.

At this time, the adhesive surface of the adhesive layer (X) is bonded to a support (not shown). On the other hand, by attaching the pressure-sensitive adhesive layer (X) so as to be sufficiently in close contact with the support, even if a force that causes unevenness is generated on the surface of the expandable base material layer (Y1) on the pressure-sensitive adhesive layer (X) side, a force that repels the pressure-sensitive adhesive layer (X) is likely to be generated. Therefore, unevenness is not easily 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 at a time with a small force at the interface P between the base (Y) of the support layer (II) and the cured resin layer (I').

The adhesive layer (X) of the laminate 1a is formed from an adhesive composition having high adhesion to the support, whereby separation can be achieved more easily at the interface P.

From the viewpoint of suppressing the transmission of stress generated by the thermally expandable particles to the pressure-sensitive adhesive layer (X), the substrate (Y) preferably has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2) as in the laminate 1b shown in fig. 1 (b).

Stress in the expandable base material layer (Y1) due to expansion of the thermally expandable particles can be suppressed by the non-expandable base material layer (Y2), and therefore is not easily transmitted to the pressure-sensitive adhesive layer (X).

Therefore, unevenness is less likely to occur on the surface of the pressure-sensitive adhesive layer (X) on the support side, and the adhesiveness between the pressure-sensitive adhesive layer (X) and the support can be maintained well without substantially changing before and after the thermal expansion treatment. As a result, irregularities are easily formed on the surface of the expandable substrate layer (Y1) on the energy ray-curable resin layer (I) side, and as a result, the interface P between the expandable substrate layer (Y1) of the support layer (II) and the cured resin layer (I') can be easily separated at a time with a small force.

As in the laminate 1b shown in fig. 1(b), the expandable base material layer (Y1) is preferably directly laminated with the energy ray-curable resin layer (I), and the pressure-sensitive adhesive layer (X) is preferably laminated on the surface of the non-expandable base material layer (Y2) opposite to the expandable base material layer (Y1).

[ laminate of second embodiment ]

Examples of the laminate according to the second embodiment of the present invention include

laminates

2a and 2b shown in fig. 2.

The

laminated bodies

2a and 2b have the following structures: the adhesive layer (X) of the support layer (II) has a structure in which the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2) are provided, the substrate (Y) is sandwiched between the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2), and the energy ray-curable resin layer (I) is directly laminated on the bonding surface of the 1 st adhesive layer (X1).

In the laminate according to the second embodiment of the present invention, the pressure-sensitive adhesive surface of the 2 nd pressure-sensitive adhesive layer (X2) is attached to a support (not shown).

In the laminate according to the second embodiment of the present invention, the substrate (Y) preferably has an expandable substrate layer (Y1) containing thermally expandable particles.

The substrate (Y) may be a single-layer structure substrate composed only of an expandable substrate layer (Y1) such as the laminate 2a shown in fig. 2(a), or may be a multilayer structure substrate having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2) such as the laminate 2b shown in fig. 2 (b).

However, from the viewpoint of forming a laminate in which the adhesion between the 2 nd pressure-sensitive adhesive layer (X2) and the support is maintained well before and after the heat expansion treatment as described above, it is preferable that the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2), as shown in fig. 2 (b).

In the laminate of the second embodiment, when the substrate (Y) having the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) is used, it is preferable that the laminate has a structure in which the 1 st pressure-sensitive adhesive layer (X1) is laminated on the surface of the expandable substrate layer (Y1) on the energy ray-curable resin layer (I) side and the 2 nd pressure-sensitive adhesive layer (X2) is laminated on the surface of the non-expandable substrate layer (Y2) on the opposite side to the expandable substrate layer (Y1), as shown in fig. 2 (b).

In the laminate of the second embodiment, the thermally expandable particles in the expandable base material layer (Y1) constituting the base material (Y) are expanded by the thermal expansion treatment, and irregularities are generated on the surface of the expandable base material layer (Y1).

Furthermore, since the 1 st adhesive layer (X1) is also pushed up by the irregularities generated on the surface of the expandable base material layer (Y1) and the irregularities are also formed on the adhesive surface of the 1 st adhesive layer (X1), the contact area between the 1 st adhesive layer (X1) and the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) in advance is reduced. As a result, the interface P between the 1 st adhesive layer (X1) of the support layer (II) and the cured resin layer (I') can be easily separated at a time with a small force.

In the laminate according to the second embodiment of the present invention, from the viewpoint of obtaining a laminate that can be separated at once and easily with a small force at the interface P, a structure in which the expandable base layer (Y1) of the base material (Y) included in the support layer (II) and the 1 st pressure-sensitive adhesive layer (X1) are directly laminated is preferable.

[ laminate of third embodiment ]

As the laminate according to the third embodiment of the present invention, a laminate 3 shown in fig. 3 can be exemplified.

The laminate 3 shown in fig. 3 includes a support layer (II) having a1 st pressure-sensitive adhesive layer (X1) as an expandable pressure-sensitive adhesive layer containing thermally expandable particles on one surface side of a substrate (Y), a2 nd pressure-sensitive adhesive layer (X2) as a non-expandable pressure-sensitive adhesive layer on the other surface side of the substrate (Y), and the laminate 3 has a structure in which the 1 st pressure-sensitive adhesive layer (X1) and an energy ray-curable resin layer (I) are directly laminated.

In the laminate 3, the pressure-sensitive adhesive surface of the 2 nd pressure-sensitive adhesive layer (X2) is bonded to a support (not shown).

The substrate (Y) of the laminate according to the third embodiment of the present invention is preferably composed of a non-expandable substrate layer.

In the laminate according to the third embodiment of the present invention, the thermally expandable particles in the 1 st adhesive layer (X1) which is an expandable adhesive layer are expanded by the thermal expansion treatment, and irregularities are generated on the surface of the 1 st adhesive layer (X1), and the contact area with the cured resin layer (I') obtained by curing the 1 st adhesive layer (X1) and the energy ray-curable resin layer (I) in advance is reduced.

On the other hand, since the substrate (Y) is laminated on the surface of the 1 st pressure-sensitive adhesive layer (X1) on the substrate (Y) side, unevenness is less likely to occur.

Therefore, irregularities are easily formed on the surface of the energy ray-curable resin layer (I) side of the 1 st adhesive layer (X1) by the thermal expansion treatment, and as a result, the interface P between the 1 st adhesive layer (X1) and the cured resin layer (I') of the support layer (II) can be easily separated at a time with a small force.

The laminate according to one embodiment of the present invention may be composed of only the support layer (II) and the energy ray-curable resin layer (I), or may have a layer other than the support layer (II) and the energy ray-curable resin layer (I). Examples of the other layer include: and an adhesive layer provided on the surface of the energy ray-curable resin layer (I) opposite to the support layer (II).

In addition, the laminate according to one embodiment of the present invention preferably does not have a thermosetting resin layer from the viewpoint of making heating unnecessary in steps other than the heat expansion treatment as much as possible. Here, the thermosetting resin layer means a layer which has thermosetting properties and is not curable by energy rays.

< various physical Properties of laminate >

(peeling force (F)₀))

From the viewpoint of sufficiently fixing the object to be sealed before the energy ray-curable resin layer (I) is cured and before the heat expansion treatment so as not to adversely affect the sealing operation, it is preferable that the adhesion between the support layer (II) and the energy ray-curable resin layer (I) is high.

From the above-described viewpoint, in the laminate according to one embodiment of the present invention, the peeling force (F) is obtained when the interface P between the support layer (II) and the energy ray-curable resin layer (I) is separated before the energy ray-curable resin layer (I) is cured and before the heat expansion treatment is performed₀) Preferably 100mN/25mm or more, more preferably 130mN/25mm or more, further preferably 160mN/25mm or more, and further preferably 50000mN/25mm or less.

The peel force (F)₀) Is a value measured by the following measurement method.

The laminate was left to stand in an environment of 23 ℃ and 50% RH (relative humidity) for 24 hours, and then an adhesive tape (product name "PL SHINE" manufactured by ledebacaceae) was attached to the surface of the energy ray-curable resin layer (I).

Then, the support layer (II) side of the laminate was bonded to a glass plate (float glass plate, 3mm (JISR 3202 product, manufactured by U-Kou K.K.) via an adhesive. Then, the end of the glass plate to which the laminate was attached was fixed to a lower chuck of a universal tensile testing machine (product name "TENSILON UTM-4-100", manufactured by Orientec Co., Ltd.).

Then, the support layer (II) of the laminate is cured with an energy rayThe pressure-sensitive adhesive tape and the support layer (II) were fixed to each other with an upper chuck of a universal tensile testing machine so that the interface P of the resin layer (I) was peeled off. Then, the peel force measured when peeling was performed at the interface P by 180 ℃ peeling method at a tensile rate of 300 mm/min in the same environment as described above based on JIS Z0237:2000 was taken as "peel force (F)₀)”。

(peeling force (F)₁))

In the laminate according to one embodiment of the present invention, the peeling force (F) at the time of separating the interface P between the support layer (II) and the cured resin layer (I ') by the heat expansion treatment after the cured resin layer (I') is obtained by curing the energy ray-curable resin layer (I) is used from the viewpoint of enabling the separation to be easily performed at the interface P with a small force, that is, at one time₁) It is usually 2000mN/25mm or less, preferably 1000mN/25mm or less, more preferably 500mN/25mm or less, further preferably 150mN/25mm or less, further preferably 100mN/25mm or less, still further preferably 50mN/25mm or less, and most preferably 0mN/25 mm.

Peeling force (F)₁) In the case of 0mN/25mm, even if the peel force is measured, the peel force may be too small to be measured.

The peel force (F)₁) Is a value measured by the following measurement method.

After the laminate was left to stand in an environment of 23 ℃ and 50% RH (relative humidity) for 24 hours, an adhesive tape (product name "PL SHINE" manufactured by linkeko corporation) was attached to the surface of the energy ray-curable resin layer (I) of the laminate.

Then, the support layer (II) side of the laminate was bonded to a glass plate (3 mm (JIS R3202, product of Kabushiki Kaisha U-Kou, float glass plate) via an adhesive.

Then, the illuminance was 215mW/cm²Light quantity 187mJ/cm²The energy ray-curable resin layer (I) is cured by irradiating with ultraviolet light 3 times under the conditions of (b) to form a cured resin layer (I'). Then, the glass plate and the laminate are expanded at maximumThe laminate was heated at the temperature for 3 minutes to expand the thermally expandable particles in the expandable base layer (Y1) of the laminate. Then, the above-mentioned peeling force (F) is applied₀) The measurement of (a) was carried out in the same manner as above, and the peel force measured when peeling was carried out at the interface P between the support layer (II) and the cured resin layer (I') under the above conditions was taken as "peel force (F)₁)”。

In addition, the peeling force (F)₁) In the measurement of (3), when the support layer (II) of the laminate is fixed by the upper chuck of the universal tensile testing machine, the cured resin layer (I') is completely separated at the interface P and cannot be fixed, the measurement is terminated, and the peeling force (F) at that time is measured₁) The sample was regarded as "0 mN/25 mm".

(adhesive force of adhesive layer (X))

In the laminate according to one embodiment of the present invention, the adhesive strength of the adhesive layer (X) (the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2)) of the support layer (II) at room temperature (23 ℃) is preferably 0.1 to 10.0N/25mm, more preferably 0.2 to 8.0N/25mm, still more preferably 0.4 to 6.0N/25mm, and still more preferably 0.5 to 4.0N/25 mm.

When the support layer (II) has the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2), the adhesive strength of the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2) is preferably in the above range, but from the viewpoint of improving the adhesion to the support and achieving separation at the interface P at a time and more easily, the adhesive strength of the 2 nd adhesive layer (X2) to be bonded to the support is preferably higher than the adhesive strength of the 1 st adhesive layer (X1).

(adhesive force of energy ray-curable resin layer (I))

In the laminate according to one embodiment of the present invention, the energy ray-curable resin layer (I) has adhesiveness on the surface on which the object to be sealed is placed (i.e., the surface opposite to the support layer (II)), from the viewpoint of improving adhesiveness to the object to be sealed.

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

In the present specification, these adhesive forces are values measured by the following measurement methods.

< measurement of adhesive force >

A PET film (product name "COSMOSHINE A4100" manufactured by Toyo Boseki K.K.) having a thickness of 50 μm was laminated on the surface of the pressure-sensitive adhesive layer (X) or the energy ray-curable resin layer (I) formed on the release film.

Then, the surface of the adhesive layer (X) or the energy ray-curable resin layer (I) was stuck to a stainless steel plate (SUS 304360 No.) as an adherend, and after standing for 24 hours in an environment of 23 ℃ at 50% RH (relative humidity), the adhesive force at 23 ℃ was measured by a 180 ° peel method at a tensile speed of 300 mm/min in the same environment based on JIS Z0237: 2000.

(Probe tack value of substrate (Y))

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

In one embodiment of the present invention, when determining whether or not a substrate is a non-adhesive substrate, if the probe tack value measured in accordance with JIS Z0237:1991 with respect to the surface of the target substrate is less than 50mN/5mm φ, the substrate is determined to be a "non-adhesive substrate". On the other hand, when the probe viscosity value is 50mN/5 mm. phi. or more, the substrate is judged to be "adhesive substrate".

The support layer (II) used in one embodiment of the present invention has a surface of the substrate (Y) with a probe tack value of generally lower than 50mN/5mm, preferably lower than 30mN/5mm, more preferably lower than 10mN/5mm, and further preferably lower than 5mN/5 mm.

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

< measurement of Probe tack value >

Cutting the substrate to be measuredAfter being a square having a side length of 10mm, the sample was left standing at 23 ℃ for 24 hours in an atmosphere of 50% RH (relative humidity), and the resultant sample was used as a test sample. The probe tack value on the test sample surface was measured in an environment of 23 ℃ and 50% RH (relative humidity) by using a tack tester (product name "NTS-4800" manufactured by Nippon Special instruments Co., Ltd.) according to JIS Z0237: 1991. Specifically, a probe made of stainless steel having a diameter of 5mm was subjected to a contact load of 0.98N/cm for 1 second²After contacting with the surface of the test sample, the force required to separate the probe from the surface of the test sample at a speed of 10 mm/sec was measured, and the obtained value was taken as the probe tack value of the test sample.

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

< support layer (II) >

The support layer (II) included in the laminate according to one embodiment of the present invention includes a base material (Y) and a pressure-sensitive adhesive layer (X), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (X) contains thermally expandable particles. As described above, the support layer (II) is a layer separated from the energy ray-curable resin layer (I) as the support object by the thermal expansion treatment, and plays a role as a so-called temporary fixing layer.

When the layer containing thermally expandable particles is included in the structure of the substrate (Y) and in the structure of the adhesive layer (X), the support layer (II) used in one embodiment of the present invention can be classified into the following forms.

Support layer (II) of the first embodiment: and a support layer (II) comprising a base material (Y) and the base material (Y) having an expandable base material layer (Y1) containing thermally expandable particles.

Support layer (II) of the second embodiment: a support layer (II) having a1 st pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles and a2 nd pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer on both sides of the substrate (Y).

[ support layer (II) of the first embodiment ]

As the support layer (II) of the first embodiment, as shown in fig. 1 to 2, there can be mentioned a layer in which the base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles.

In the support layer (II) of the first embodiment, the adhesive layer (X) is preferably a non-swelling adhesive layer in view of being able to be separated at the interface P at once and easily with a small force.

Specifically, in the support layer (II) included in the

laminate

1a or 1b shown in fig. 1, the pressure-sensitive adhesive layer (X) is preferably a non-expandable pressure-sensitive adhesive layer.

In the support layer (II) included in the

laminates

2a and 2b shown in fig. 2, both the 1 st pressure-sensitive adhesive layer (X1) and the 2 nd pressure-sensitive adhesive layer (X2) are preferably non-expandable pressure-sensitive adhesive layers.

By providing the base material (Y) with the expandable base material layer (Y1) as in the support layer (II) of the first embodiment, the adhesive layer (X) does not have to have expandability, and is not limited to the composition, configuration, and process for imparting expandability. Thus, in designing the pressure-sensitive adhesive layer (X), it is possible to realize a design that gives priority to desired performances other than expansibility, such as adhesiveness and productivity and economy, and thus it is possible to improve the degree of freedom in designing the pressure-sensitive adhesive layer (X).

The thickness of the base material (Y) before the heat expansion treatment of the support layer (II) of the first embodiment is preferably 10 to 1000. mu.m, more preferably 20 to 700. mu.m, still more preferably 25 to 500. mu.m, and still more preferably 30 to 300. mu.m.

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

In the present specification, when the support layer (II) has a plurality of adhesive layers (X) as shown in fig. 2, the "thickness of the adhesive layer (X)" represents the thickness of each adhesive layer (in fig. 2, the thickness of the 1 st adhesive layer (X1) and the thickness of the 2 nd adhesive layer (X2) are represented).

In the present specification, the thickness of each layer constituting the laminate represents a value measured by the method described in examples.

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

When the thickness ratio is 1000 or less, a laminate which can be separated at once and easily with a small force, that is, by a small force at the interface P between the support layer (II) and the cured resin layer (I') can be obtained by the heat expansion treatment.

The thickness ratio is preferably 0.2 or more, more preferably 0.5 or more, further preferably 1.0 or more, and further preferably 5.0 or more.

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

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

[ support layer (II) of the second embodiment ]

As the support layer (II) of the second embodiment, there can be mentioned a layer having, on both sides of the substrate (Y), a1 st pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer containing thermally expandable particles and a2 nd pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer, as shown in fig. 3.

In the support layer (II) of the second embodiment, the 1 st adhesive layer (X1) as the expandable adhesive layer is in direct contact with the energy ray-curable resin layer (I).

In the support layer (II) of the second embodiment, the substrate (Y) is preferably a non-swelling substrate. The non-expandable substrate is preferably a material composed only of the non-expandable substrate layer (Y2).

In the support layer (II) of the second embodiment, the thickness ratio [ (X1)/(X2) ] of the 1 st pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer before the heat expansion treatment to the 2 nd pressure-sensitive adhesive layer (X2) which is a non-expandable pressure-sensitive adhesive layer is preferably 0.1 to 80, more preferably 0.3 to 50, and still more preferably 0.5 to 15.

In the support layer (II) of the second embodiment, the thickness ratio [ (X1)/(Y) ] of the 1 st pressure-sensitive adhesive layer (X1) which is an expandable pressure-sensitive adhesive layer before the heat expansion treatment to the substrate (Y) is preferably 0.05 to 20, more preferably 0.1 to 10, and further preferably 0.2 to 3.

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

[ Heat-expandable particles ]

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

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

The average particle diameter of the thermally expandable particles before expansion is referred to as the volume median diameter (D)₅₀) In the particle distribution of the thermally expandable particles before expansion measured by a laser diffraction particle size distribution measuring apparatus (for example, a product name "Mastersizer 3000" manufactured by Malvern), the cumulative volume frequency calculated from the particles having a small particle size among the thermally expandable particles before expansion corresponds to a particle size of 50%.

The thermally expandable particles used in one embodiment of the present invention have a 90% particle diameter (D) before expansion at 23 ℃₉₀) Preferably 10 to 150 μm, more preferably 20 to 100 μm, further preferably 25 to 90 μm, and further preferably 30 to 80 μm.

Need to make sure thatThe thermally expandable particles had a particle diameter of 90% (D) before expansion₉₀) The particle size distribution of the thermally expandable particles before expansion measured by a laser diffraction particle size distribution measuring apparatus (for example, a product name "Mastersizer 3000" manufactured by Malvern) is a particle size in which the cumulative volume frequency calculated from the particles having a small particle size among the thermally expandable particles before expansion corresponds to 90%.

The thermally expandable particles used in one embodiment of the present invention may be particles that do not expand when the sealing material is cured and that have an expansion start temperature (t) higher than the curing temperature of the sealing material, and specifically, thermally expandable particles whose expansion start temperature (t) is adjusted to 60 to 270 ℃ are preferable. The expansion start temperature (t) may be appropriately selected depending on the curing temperature of the sealing material to be used.

In the present specification, the expansion start temperature (t) of the thermally expandable particles is a value measured by the method described in examples.

The thermally expandable particles are preferably a microencapsulated blowing agent containing an outer shell made of a thermoplastic resin and an encapsulated component encapsulated by the outer shell and vaporized when heated to a predetermined temperature.

Examples of the thermoplastic resin constituting the shell of the microencapsulated blowing agent include: vinylidene chloride-acrylonitrile copolymers, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, and the like.

Examples of the inner package component enclosed by the outer shell include: propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclotridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, isotridecyl, 4-methyldodecane, isotetradecane, isopentadecane, isohexadecane, 2,4,4,6,8, 8-heptamethylnonane, isoheptadecane, isooctadecane, isononane, 2,6,10, 14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, pentadecylcyclohexane, hexadecylcyclohexane, isohexadecane, isopentadecane, isopentane, hexadecane, heptadecane, Heptadecylcyclohexane, octadecylcyclohexane, and the like.

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

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

The maximum volume expansion coefficient when heated to a temperature equal to or higher than the expansion starting 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, even more preferably 2.5 to 60 times, and even more preferably 3 to 40 times.

< intumescent base Material layer (Y1) >

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

From the viewpoint of improving interlayer adhesion between the expandable base material layer (Y1) and another layer to be laminated, the surface of the expandable base material layer (Y1) may be subjected to a surface treatment such as an oxidation method or a roughening method, an easy adhesion treatment, or an undercoating treatment.

Examples of the oxidation method include: examples of the method of forming the concavities and convexities include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet type), hot air treatment, ozone treatment, and ultraviolet irradiation treatment: sand blasting, solvent treatment, and the like.

In one embodiment of the present invention, the expandable substrate layer (Y1) preferably satisfies the following condition (1).

Condition (1): the storage modulus E' (t) of the expandable base layer (Y1) was 1.0X 10 at the expansion initiation temperature (t) of the thermally expandable particles⁷Pa or less.

In the present specification, the storage modulus E' of the expandable base material layer (Y1) at a given temperature is a value measured by the method described in examples.

The condition (1) may be an index representing the rigidity of the expandable base material layer (Y1) immediately before the expansion of the thermally expandable particles.

In order to easily separate the support layer (II) from the cured resin layer (I') with a small force at the interface P, it is necessary that the surface of the support layer (II) on the side laminated with the energy ray-curable resin layer (I) is easily uneven when heated to a temperature equal to or higher than the expansion start temperature (t).

That is, the expandable substrate layer (Y1) satisfying the above condition (1) expands and becomes sufficiently large at the expansion start temperature (t), and irregularities are likely to be formed on the surface of the support layer (II) on the side on which the energy ray curable resin layer (I) is laminated.

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

From the above viewpoint, the storage modulus E' (t) of the expandable base material layer (Y1) defined in the condition (1) is preferably 9.0 × 10⁶Pa or less, more preferably 8.0X 10⁶Pa or less, more preferably 6.0X 10⁶Pa or less, more preferably 4.0X 10⁶Pa or less.

The storage modulus E' (t) of the expandable base layer (Y1) defined in the condition (1) is preferably 1.0 × 10 from the viewpoint of suppressing the flow of the thermally expandable particles after expansion, improving the shape retaining property of the irregularities formed on the surface of the support layer (II) on the side where the energy ray curable resin layer (I) is laminated, and enabling easier separation with a small force at the interface P, that is, with a small force³Pa or more, more preferably 1.0X 10⁴Pa or more, preferably 1.0X 10⁵Pa or above.

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

The resin composition (y) may contain a base material additive as needed within a range not to impair the effects of the present invention.

Examples of the additive for a base material include: light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, colorants, and the like.

These additives for base materials may be used alone or in combination of two or more.

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

The content of the thermally expandable particles is preferably 1 to 40 mass%, more preferably 5 to 35 mass%, still more preferably 10 to 30 mass%, and still more preferably 15 to 25 mass% with respect to the total amount (100 mass%) of the expandable base layer (Y1) or the total amount (100 mass%) of the active ingredients of the resin composition (Y).

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

That is, even if the resin contained in the resin composition (Y) is an adhesive resin, the adhesive resin and the polymerizable compound may be subjected to a polymerization reaction in the process of forming the expandable base layer (Y1) from the resin composition (Y), and the resulting resin may be a non-adhesive resin, and the expandable base layer (Y1) containing the resin may be non-adhesive.

The weight average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably 1000 to 100 ten thousand, more preferably 1000 to 70 ten thousand, and still more preferably 1000 to 50 ten thousand.

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

The content of the resin is preferably 50 to 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, based on the total amount (100% by mass) of the swellable base layer (Y1) or the total amount (100% by mass) of the active ingredient of the resin composition (Y).

From the viewpoint of forming the expandable base layer (Y1) satisfying the condition (1), the resin contained in the resin composition (Y) preferably contains at least one selected from the group consisting of an acrylic urethane resin and an olefin resin.

The acrylic urethane resin is preferably the following resin (U1).

An acrylic urethane resin (U1) obtained by polymerizing a Urethane Prepolymer (UP) and a vinyl compound containing a (meth) acrylate.

(acrylic urethane resin (U1))

As the Urethane Prepolymer (UP) forming the main chain of the acrylic urethane-based resin (U1), a reaction product of a polyol and a polyisocyanate is exemplified.

The Urethane Prepolymer (UP) is preferably a prepolymer obtained by further performing a chain extension reaction using a chain extender.

Examples of the polyol to be a raw material of the Urethane Prepolymer (UP) include: alkylene polyols, ether polyols, ester polyols, esteramide polyols, ester-ether polyols, carbonate polyols, and the like.

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

The polyol used in one embodiment of the present invention is preferably a diol, more preferably an ester diol, an alkylene diol, and a carbonate diol, and even more preferably an ester diol or a carbonate diol.

Examples of the ester diol include polycondensates of one or more selected from the following diols and one or more selected from the following dicarboxylic acids and anhydrides thereof: alkane diols such as 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, and 1, 6-hexanediol, and alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; the dicarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4-diphenyldicarboxylic acid, diphenylmethane-4, 4' -dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chlorendic acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1, 3-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, and the like.

Specific examples thereof include: polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate 1, 6-hexanediol, polyhexamethylene isophthalate 1, 6-hexanediol, polyhexamethylene glycol adipate glycol, polyethylene glycol propylene adipate glycol, polybutylene adipate 1, 6-hexanediol, polydiethylene glycol adipate glycol, poly (polytetramethylene ether) adipate glycol, poly (3-methylpentaneadipate) glycol, polyethylene glycol azelate glycol, polyethylene glycol sebacate glycol, polybutylene azelate glycol, polybutylene sebacate glycol, and polybutylene terephthalate glycol.

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

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

Examples of the polyisocyanate to be used as a raw material of the Urethane Prepolymer (UP) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

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

These polyisocyanates may be modified trimethylolpropane adduct type, biuret type modified by reaction with water, or isocyanurate type modified containing an isocyanurate ring.

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

Examples of the alicyclic diisocyanate include: 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate and the like, preferably isophorone diisocyanate (IPDI).

In one embodiment of the present invention, the Urethane Prepolymer (UP) forming the main chain of the acrylic urethane resin (U1) is preferably a linear urethane prepolymer having an ethylenically unsaturated group at both ends, which is a reaction product of a diol and a diisocyanate.

As a method for introducing an ethylenically unsaturated group into both ends of the linear urethane prepolymer, a method in which an NCO group at the end of a linear urethane prepolymer obtained by reacting a diol and a diisocyanate compound is reacted with a hydroxyalkyl (meth) acrylate is exemplified.

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

The vinyl compound forming the side chain of the acrylic urethane resin (U1) contains at least (meth) acrylate.

The (meth) acrylate is preferably at least one selected from the group consisting of alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates, and more preferably an alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are used in combination.

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

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

In addition, examples of the hydroxyalkyl (meth) acrylate include the same hydroxyalkyl (meth) acrylate as described above for introducing an ethylenically unsaturated group to both ends of the linear urethane prepolymer.

Examples of the vinyl compound other than the (meth) acrylate include: aromatic hydrocarbon vinyl compounds such as styrene, α -methylstyrene and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; polar group-containing monomers such as vinyl acetate, vinyl propionate, (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and (meth) acrylamide; and so on.

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

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

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

In the acrylic urethane resin (U1) used in one embodiment of the present invention, the content ratio [ (U11)/(U12) ] of the structural unit (U11) derived from the Urethane Prepolymer (UP) to the structural unit (U12) derived from the vinyl compound is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, further preferably 30/70 to 60/40, and further preferably 35/65 to 55/45 in terms of mass ratio.

(olefin resin)

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

The olefin monomer is preferably an α -olefin having 2 to 8 carbon atoms, and specific examples thereof include: ethylene, propylene, butene, isobutylene, 1-hexene, and the like.

Of these, ethylene and propylene are preferred.

Specific examples of the olefin-based resin include: ultra-low density polyethylene (VLDPE, density: 880 kg/m)³Above and below 910kg/m³) Low density polyethylene (LDPE, density: 910kg/m³Above and below 915kg/m³) Medium density polyethylene (MDPE, density: 915kg/m³Above and below 942kg/m³) High density polyethylene (HDPE, density: 942kg/m³The above), linear low-density polyethylene, and other polyethylene resins; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymers; olefin-based elastomers (TPO); poly (4-methyl-1-pentene) (PMP); ethylene-vinyl acetate copolymers (EVA); ethylene vinyl alcohol copolymers (EVOH); olefin terpolymers such as ethylene-propylene- (5-ethylidene-2-norbornene); and so on.

In one embodiment of the present invention, the olefin-based resin may be a modified olefin-based resin further modified with one or more kinds of modification selected from acid modification, hydroxyl modification, and acrylic modification.

For example, as an acid-modified olefin-based resin obtained by acid-modifying an olefin-based resin, there can be mentioned a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an acid anhydride thereof onto the above-mentioned unmodified olefin-based resin.

Examples of the unsaturated carboxylic acid or anhydride thereof include: maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.

The unsaturated carboxylic acid or anhydride thereof may be used alone or in combination of two or more.

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

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

Examples of the alkyl (meth) acrylate include the same compounds as those which can be selected as the monomer (a 1') described later.

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

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

(resins other than the urethane acrylate resin and the olefin resin)

In one embodiment of the present invention, the resin composition (y) may contain a resin other than the acrylic urethane resin and the olefin resin within a range not to impair the effects of the present invention.

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 copolymers; cellulose triacetate; a polycarbonate; polyurethanes that do not belong to the group of acrylic urethane resins; polysulfones; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; a polyamide-based resin; acrylic resin; fluorine-based resins, and the like.

Among these, from the viewpoint of forming the expandable base layer (Y1) satisfying the above condition (1), it is preferable that the resin composition (Y) contains a small amount of resin other than the acrylic urethane resin and the olefin resin.

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 less than 20 parts by mass, still more preferably less than 10 parts by mass, yet still more preferably less than 5 parts by mass, and yet still more preferably less than 1 part by mass, based on 100 parts by mass of the total amount of the resins contained in the resin composition (y).

(solvent-free resin composition (y1))

The resin composition (y) used in one embodiment of the present invention is a solvent-free resin composition (y1) which contains an oligomer having an ethylenically unsaturated group and a weight average molecular weight (Mw) of 50,000 or less, an energy ray-polymerizable monomer, and the thermally expandable particles, and which contains no solvent.

The solvent-free resin composition (y1) does not contain a solvent, but the energy ray-polymerizable monomer contributes to improvement in plasticity of the oligomer.

By irradiating the coating film formed from the solvent-free resin composition (Y1) with an energy ray, the expandable base layer (Y1) satisfying the above condition (1) can be easily formed.

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

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

The oligomer may be any oligomer having an ethylenically unsaturated group with a weight average molecular weight of 50,000 or less in the resin contained in the resin composition (y), and is preferably the Urethane Prepolymer (UP).

As the oligomer, a modified olefin-based resin having an ethylenically unsaturated group can be used.

The total content of the oligomer and the energy ray-polymerizable monomer in the solvent-free resin composition (y1) is preferably 50 to 99% 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, based on the total amount (100% by mass) of the solvent-free resin composition (y 1).

Examples of the energy ray-polymerizable monomer include: alicyclic polymerizable compounds such as isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, and tricyclodecanyl acrylate; aromatic polymerizable compounds such as phenyl hydroxypropyl acrylate, benzyl acrylate, and phenol ethylene oxide-modified acrylate; heterocyclic polymerizable compounds such as tetrahydrofurfuryl (meth) acrylate, morpholine acrylate, N-vinylpyrrolidone and N-vinylcaprolactam.

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

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

In one embodiment of the present invention, the solventless resin composition (y1) is preferably further blended with a photopolymerization initiator.

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

Examples of the photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, butanedione, 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 still more preferably 0.02 to 3 parts by mass, based on the total amount (100 parts by mass) of the oligomer and the energy ray-polymerizable monomer.

< non-expandable substrate layer (Y2) >

Examples of the material for forming the non-expandable base layer (Y2) constituting the base material (Y) include: paper, resin, metal, and the like can be appropriately selected according to the use of the laminate according to one embodiment of the present invention.

Examples of the paper include: thin paper, medium paper, high-quality paper, impregnated paper, coated paper, art paper, parchment paper, glassine paper and the like.

Examples of the resin include: polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymers; cellulose triacetate; a polycarbonate; polyurethane resins such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfones; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; a polyamide-based resin; acrylic resin; fluorine-based resins, and the like.

Examples of the metal include: aluminum, tin, chromium, titanium, and the like.

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

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

Examples of the method for forming the metal layer include: a method of depositing the above metal by a PVD method such as vacuum deposition, sputtering, or ion plating, or a method of attaching a metal foil made of the above metal using a conventional adhesive, and the like.

Here, in one embodiment of the present invention, from the viewpoint of suppressing formation of irregularities on the surface of the expandable base material layer (Y1) on the non-expandable base material layer (Y2) side when the expandable particles contained in the expandable base material layer (Y1) expand, and preferentially forming irregularities on the surface of the expandable base material layer (Y1) on the pressure-sensitive adhesive layer (X1) side, it is preferable that the non-expandable base material layer (Y2) has a rigidity of a degree such that deformation does not occur due to expansion of the expandable particles. Specifically, the storage modulus E' (t) of the non-expandable base material layer (Y2) at the temperature (t) at which expansion of the expandable particles starts is preferably 1.1 × 10⁷Pa or above.

In the case where the non-expandable base material layer (Y2) contains a resin, from the viewpoint of improving interlayer adhesion between the non-expandable base material layer (Y2) and another layer to be laminated, the surface of the non-expandable base material layer (Y2) may be subjected to a surface treatment by an oxidation method, a roughening method, or the like, an easy adhesion treatment, or an undercoating treatment, as in the case of the expandable base material layer (Y1).

When the non-expandable substrate layer (Y2) contains a resin, the resin may be contained, and the substrate additive that may be contained in the resin composition (Y) may be contained.

The non-expandable substrate layer (Y2) is a non-expandable layer that can be determined by the above method.

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

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

However, the non-expandable substrate layer (Y2) preferably does not contain thermally expandable particles. When the non-expandable base material layer (Y2) contains heat-expandable particles, the smaller the content thereof, the more preferable the specific content of the heat-expandable particles is, the less than 3 mass%, preferably less than 1 mass%, more preferably less than 0.1 mass%, further preferably less than 0.01 mass%, and still further preferably less than 0.001 mass% with respect to the total amount (100 mass%) of the non-expandable base material layer (Y2).

< adhesive layer (X) >

The adhesive layer (X) included in the support layer (II) used in one embodiment of the present invention may be formed of an adhesive composition (X) containing an adhesive resin.

The pressure-sensitive adhesive composition (x) may further contain a pressure-sensitive adhesive additive such as a crosslinking agent, a tackifier, a polymerizable compound, or a polymerization initiator, if necessary.

The components contained in the pressure-sensitive adhesive composition (x) will be described below.

Even when the support layer (II) has the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2), the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2) may be formed of an adhesive composition (X) containing the following components.

(adhesive resin)

As the adhesive resin used in one embodiment of the present invention, it is preferable that the resin alone has adhesive properties and is a polymer having a weight average molecular weight (Mw) of 1 ten thousand or more.

The weight average molecular weight (Mw) of the pressure-sensitive adhesive resin used in one embodiment of the present invention is preferably 1 to 200 ten thousand, more preferably 2 to 150 ten thousand, and even more preferably 3 to 100 ten thousand, from the viewpoint of improving the pressure-sensitive adhesive force.

Specific examples of the adhesive resin include: rubber-based resins such as acrylic resins, urethane-based resins and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether-based resins.

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

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

In one embodiment of the present invention, the pressure-sensitive adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesion.

In the case of using the support layer (II) having the 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2), the 1 st adhesive layer (X1) in contact with the energy ray-curable resin layer (I) is made of an acrylic resin, whereby irregularities can be easily formed on the surface of the 1 st adhesive layer (X1).

The content of the acrylic resin in the adhesive resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass, based on the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (X) or the adhesive layer (X).

The content of the adhesive resin is preferably 35 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 60 to 98% by mass, and even more preferably 70 to 95% by mass, based on 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).

(crosslinking agent)

In one embodiment of the present invention, when the adhesive composition (x) contains an adhesive resin having a functional group, it preferably further contains a crosslinking agent.

The crosslinking agent is a component that reacts with an adhesive resin having a functional group to crosslink the adhesive resins with each other with the functional group as a crosslinking starting point.

Examples of the crosslinking agent include: isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and the like.

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

Among these crosslinking agents, isocyanate-based crosslinking agents are preferable from the viewpoint of improving cohesive force to improve adhesive force, and from the viewpoint of easiness in acquisition.

The content of the crosslinking agent may be appropriately adjusted depending on the number of functional groups contained in the adhesive resin, but is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the adhesive resin having functional groups.

(tackifier)

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

In the present specification, the "tackifier" is a component which is different from the above adhesive resin, and is an oligomer having a weight average molecular weight (Mw) of less than 1 ten thousand among components which increase the adhesive force of the above adhesive resin in an auxiliary manner.

The thickener has a weight average molecular weight (Mw) of preferably 400 to 9000, more preferably 500 to 8000, and further preferably 800 to 5000.

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

The softening point of the thickener is preferably 60 to 170 ℃, more preferably 65 to 160 ℃, and further preferably 70 to 150 ℃.

In the present specification, the "softening point" of the tackifier means a value measured in accordance with JIS K2531.

The tackifier may be used alone, or two or more different in softening point, structure, and the like may be used in combination.

Also, in the case where two or more kinds of tackifiers are used, it is preferable that the weighted average of the softening points of the plurality of tackifiers falls within the above range.

The content of the thickener is preferably 0.01 to 65% by mass, more preferably 0.1 to 50% by mass, even more preferably 1 to 40% by mass, and even more preferably 2 to 30% by mass, based on 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).

(additive for adhesive)

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

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

These additives for adhesives may be used alone or in combination of two or more.

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

In the case of using the support layer (II) of the second embodiment having the 1 st pressure-sensitive adhesive layer (X1) as the expandable pressure-sensitive adhesive layer, the material for forming the 1 st pressure-sensitive adhesive layer (X1) as the expandable pressure-sensitive adhesive layer may be formed of an expandable pressure-sensitive adhesive composition (X11) further containing thermally expandable particles in the pressure-sensitive adhesive composition (X).

The thermally expandable particles are as described above.

The content of the thermally expandable particles is preferably 1 to 70 mass%, more preferably 2 to 60 mass%, even more preferably 3 to 50 mass%, and even more preferably 5 to 40 mass% with respect to the total amount (100 mass%) of the active ingredient of the expandable adhesive composition (x11) or the total amount (100 mass%) of the expandable adhesive layer.

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

When the thermally expandable particles are contained, the content thereof is preferably as small as possible, and is 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, based on 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).

In the case of using a support layer (II) having the 1 st pressure-sensitive adhesive layer (X1) and the 2 nd pressure-sensitive adhesive layer (X2) as the non-expandable pressure-sensitive adhesive layers as in the

laminates

2a and 2b shown in fig. 2, the shear storage modulus G' (23) at 23 ℃ of the 1 st pressure-sensitive adhesive layer (X1) as the non-expandable pressure-sensitive adhesive layer is preferably 1.0 × 10⁸Pa or lessMore preferably 5.0X 10⁷Pa or less, more preferably 1.0X 10⁷Pa or less.

The shear storage modulus G' (23) of the 1 st adhesive layer (X1) as a non-expandable adhesive layer was 1.0X 10⁸When Pa is less, for example, in the case of the

laminate

2a, 2b shown in fig. 2, irregularities are easily formed on the surface of the 1 st pressure-sensitive adhesive layer (X1) in contact with the cured resin layer (I') by expansion of the thermally expandable particles in the expandable base material layer (Y1) by the thermal expansion treatment.

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

The shear storage modulus G' (23) at 23 ℃ of the 1 st pressure-sensitive adhesive layer (X1) as a non-expandable pressure-sensitive adhesive layer is preferably 1.0 × 10⁴Pa or more, more preferably 5.0X 10⁴Pa or more, preferably 1.0X 10⁵Pa or above.

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

From the viewpoint of achieving the above light transmittance, when the base material (Y) and the pressure-sensitive adhesive layer (X) of the support layer (II) contain a colorant, the content thereof is preferably adjusted within a range not to impair the effects of the present invention.

When the colorant is contained, the content thereof is preferably as small as possible, and is preferably less than 1 mass%, more preferably less than 0.1 mass%, even more preferably less than 0.01 mass%, even more preferably less than 0.001 mass%, based on 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), and the content of the colorant in the substrate (Y) is preferably less than 1 mass%, more preferably less than 0.1 mass%, even more preferably less than 0.01 mass%, even more preferably less than 0.001 mass%, based on the total amount (100 mass%) of the active ingredients of the resin composition (Y) or the total amount (100 mass%) of the substrate (Y).

< 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, and is, for example, a layer formed from an energy ray-curable resin composition containing an energy ray-curable component (a).

[ energy ray-curable component (a) ]

The energy ray-curable component (a) is a component which is cured by irradiation with an energy ray.

Examples of the energy ray-curable component (a) include: a polymer (a1) (hereinafter also referred to simply as "polymer (a 1)") having an energy ray-curable double bond and a weight average molecular weight (Mw) of 80000 to 2000000, a compound (a2) (hereinafter also referred to simply as "compound (a 2)") having an energy ray-curable double bond and a molecular weight of 100 to 80000, and the like.

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

(Polymer (a1))

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

Examples of the polymer (a1) include: an acrylic resin (a1-1) obtained by polymerizing an acrylic polymer (a11) having a functional group X capable of reacting with a group of another compound and an energy ray-curable compound (a12) having a group Y reactive with the functional group X and an energy ray-curable double bond.

The polymer (a1) may be used alone or in combination of two or more.

Acrylic Polymer (a11)

Examples of the functional group X of the acrylic polymer (a11) include: at least one member selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a substituted amino group (a group in which 1 or 2 hydrogen atoms on the amino group are substituted with a group other than a hydrogen atom), and an epoxy group.

Examples of the acrylic polymer (a11) include: the polymer obtained by copolymerizing the acrylic monomer having the functional group X and the acrylic monomer not having the functional group X may be a polymer obtained by further copolymerizing a monomer other than the acrylic monomer (non-acrylic monomer) in addition to these monomers. The acrylic polymer (a11) may be a random copolymer or a block copolymer.

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

Examples of the acrylic monomer having the functional group X include: hydroxyl-containing monomers, carboxyl-containing monomers, amino-containing monomers, substituted amino-containing monomers, epoxy-containing monomers and the like.

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

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

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

Examples of the acrylic monomer having no functional group X include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, And alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).

Further, as the acrylic monomer having no functional group X, for example: alkoxyalkyl group-containing (meth) acrylates such as methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate; aromatic group-containing (meth) acrylates including aryl (meth) acrylates such as phenyl (meth) acrylate; non-crosslinkable (meth) acrylamide and derivatives thereof; and (meth) acrylic esters having a non-crosslinkable tertiary amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate.

Examples of the non-acrylic monomer include: olefins such as ethylene and norbornene; vinyl acetate; styrene, and the like.

In the acrylic polymer (a11), the content of the structural unit derived from the acrylic monomer having the functional group X is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 3 to 30% by mass, relative to the total amount of the structural units constituting the polymer. When the content of the structural unit is in the above range, the content of the energy ray-curable double bond in the resulting acrylic resin (a1-1) can be easily adjusted to 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: at least one member selected from the group consisting of isocyanate group, epoxy group and carboxyl group, and among these groups, isocyanate group is preferable. When the energy ray-curable compound (a12) has an isocyanate group, the isocyanate group is likely to react with a hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the functional group.

The number of the energy ray-curable double bonds of the energy ray-curable compound (a12) is preferably 1 to 5, more preferably 1 to 3 per 1 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, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, 1- (bisacryloxymethyl) ethyl isocyanate; a diisocyanate compound or a polyisocyanate compound, and a acryloyl monoisocyanate compound obtained by reacting hydroxyethyl (meth) acrylate; and an acryloyl group monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with a polyol compound and hydroxyethyl (meth) acrylate. Among these compounds, 2-methacryloyloxyethyl isocyanate is preferable.

In the acrylic resin (a1-1), the proportion of the content of the energy ray-curable double bonds derived from the energy ray-curable compound (a12) is preferably 20 to 120 mol%, more preferably 5 to 100 mol%, and still more preferably 50 to 100 mol% with respect to the content of the functional group X derived from the acrylic polymer (a 11). When the ratio is within the above range, the adhesive strength of the cured resin layer (I') formed by curing becomes larger. In the case where the energy ray-curable compound (a12) is a monofunctional compound (having 1 group in the molecule), the upper limit of the proportion of the above content is 100 mol%, but in the case where the energy ray-curable compound (a12) is a polyfunctional compound (having 2 or more groups in the molecule of 1), the upper limit of the proportion of the above content may exceed 100 mol%.

The content of the acrylic resin (a1-1) is preferably 1 to 40 mass%, more preferably 2 to 30 mass%, and even more preferably 3 to 20 mass% with respect to the total amount (100 mass%) of the active ingredients of the energy ray-curable resin composition or the total amount (100 mass%) of the energy ray-curable resin layer (I).

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

The polymer (a1) may be a polymer at least a part of which is crosslinked by a crosslinking agent (e) described later, or may be a polymer that is not crosslinked.

(Compound (a2))

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

The energy ray-curable double bond of the compound (a2) is preferably a (meth) acryloyl group, vinyl group or the like.

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, phenol resins having an energy ray-curable double bond, and the like.

The 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, oligomers, and the like, preferably an acrylate compound having a (meth) acryloyl group.

Examples of the acrylate-based compound include: 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, polyethylene glycol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxypolyethoxy) phenyl ] propane, ethoxylated bisphenol A di (meth) acrylate, 2-bis [4- ((meth) acryloyloxydiethoxy) phenyl ] propane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, 2-bis [4- ((meth) acryloyloxypolypropoxy) phenyl ] propane, tricyclodecanedimethanol di (meth) acrylate (tricyclodecanedimethylol di (meth) acrylate), 1, 10-decanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol, Difunctional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipropylene glycol di (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-bis [4- ((meth) acryloyloxyethoxy) phenyl ] propane, neopentyl glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1, 3-di (meth) acryloyloxypropane; polyfunctional (meth) acrylates such as tris (2- (meth) acryloyloxyethyl) isocyanurate, epsilon-caprolactone-modified tris- (2- (meth) acryloyloxyethyl) isocyanurate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; and polyfunctional (meth) acrylate oligomers such as urethane (meth) acrylate oligomers.

Examples of the epoxy resin having an energy ray-curable double bond and the phenol resin having an energy ray-curable double bond include resins described in paragraph 0043 of "jp 2013-194102 a". Such a resin is also a resin constituting a thermosetting component (f) described later, but is treated as the compound (a2) in the present invention.

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

The content of the compound (a2) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 20% by mass, 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).

[ Polymer (b) having no energy ray-curable double bond ]

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

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

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

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

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

Examples of the alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, myristyl (meth) acrylate, And alkyl (meth) acrylates having a chain structure in which the alkyl group constituting the alkyl ester is a carbon number of 1 to 18, such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, and octadecyl (meth) acrylate (stearyl (meth) acrylate).

Examples of the (meth) acrylate having a cyclic skeleton include: cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; cycloalkenyl (meth) acrylates such as dicyclopentenyl (meth) acrylate; and cycloalkenyloxyalkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate.

Examples of the glycidyl group-containing (meth) acrylate include: glycidyl (meth) acrylate, and the like.

Examples of the hydroxyl group-containing (meth) acrylate include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

Examples of the substituted amino group-containing (meth) acrylate include: n-methylaminoethyl (meth) acrylate, and the like.

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

The polymer (b) may be a polymer at least a part of which is crosslinked by the crosslinking agent (e), or may be a polymer which is not crosslinked.

Examples of the polymer (b) at least a part of which is crosslinked by the crosslinking agent (e) include: a polymer obtained by reacting the reactive functional group in the polymer (b) with the crosslinking agent (e).

The reactive functional group may be appropriately selected depending on the kind of the crosslinking agent (e), and the like, and is not particularly limited. For example, when the crosslinking agent (e) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group, and among these functional groups, a hydroxyl group having high reactivity with an isocyanate group is preferable. When the crosslinking agent (e) is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amino group, and an amide group, and among these functional groups, a carboxyl group having high reactivity with an epoxy group is preferable. In view of preventing corrosion of circuits of the semiconductor wafer and the semiconductor chip, the reactive functional group is preferably a group other than a carboxyl group.

Examples of the polymer (b) having the reactive functional group include polymers obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), a monomer having the reactive functional group may be used as either or both of the acrylic monomer and the non-acrylic monomer listed as the monomer constituting the polymer. Examples of the polymer (b) having a hydroxyl group as a reactive functional group include, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth) acrylate, and in addition to the above, a polymer obtained by polymerizing a monomer in which 1 or 2 or more hydrogen atoms in the above-mentioned acrylic monomer or non-acrylic monomer are substituted with the above-mentioned reactive functional group.

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

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

The energy ray-curable resin composition includes a composition containing either one or both of the polymer (a1) and the compound (a2), and when the compound (a2) is contained, it is preferable that the composition further contains a polymer (b).

The total content of the energy ray-curable component (a) and the polymer (b) is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 15 to 70 mass%, based on the total amount (100 mass%) of the active components of the energy ray-curable resin composition or the total amount (100 mass%) of the energy ray-curable resin layer (I). When the total content is within the above range, the energy ray curability is more preferable.

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 preferably 3 to 160 parts by mass, more preferably 6 to 130 parts by mass, based on 100 parts by mass of the energy ray-curable 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 may contain, in addition to the energy ray-curable component (a) and the polymer (b), one or more selected from a photopolymerization initiator (c), a coupling agent (d), a crosslinking agent (e), a colorant (g), a thermosetting component (f), a curing accelerator (g), a filler (h), and a general-purpose additive (z) according to the purpose. For example, by using an energy ray-curable resin composition containing an energy ray-curable component (a) and a thermosetting component (f), the adhesion of the formed energy ray-curable resin layer (I) to an adherend is improved by heating, and the strength of the cured resin layer (I') formed from the energy ray-curable resin layer (I) is also improved.

[ photopolymerization initiator (c) ]

Examples of the photopolymerization initiator (c) include: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ether, and the like; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethane-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; thioether compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone compounds such as benzophenone, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), and the like; a peroxide compound; diketone compounds such as butanedione; a benzyl group; a dibenzyl group; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like. In addition, it is also possible to use: quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like.

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 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and still more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the energy ray-curable compound (a).

[ coupling agent (d) ]

By using a compound having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (d), the adhesion of the energy ray-curable resin layer (I) can be improved, and the water resistance of the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) can be improved without impairing the heat resistance thereof.

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 a functional group of the energy ray-curable component (a), the polymer (b), or the like, and more preferably a silane coupling agent.

Examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, Bis (3-triethoxysilylpropyl) tetrasulfide, 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 preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the energy ray-curable component (a) and the polymer (b). When the content of the coupling agent (d) is not less than the lower limit, the effects of improving the dispersibility of the filler in the resin, improving the adhesiveness of the energy ray-curable resin layer (I), and the like can be more remarkably obtained, and when the content is not more than the upper limit, the occurrence of gas leakage can be suppressed.

[ crosslinking agent (e) ]

The initial adhesion and cohesion of the energy ray-curable resin layer (I) can be adjusted by crosslinking the energy ray-curable component (a), the polymer (b), and the like with the crosslinking agent (e).

The crosslinking agent (e) may be used alone or in combination of two or more.

Examples of the crosslinking agent (e) include: an organic polyvalent isocyanate compound, an organic polyvalent imine compound, a metal chelate-based crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine-based crosslinking agent (a crosslinking agent having an aziridine group), and the like.

Examples of the organic polyisocyanate compound include: an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be collectively referred to simply as "aromatic polyisocyanate compound or the like"); trimers, isocyanurates and adducts of the above aromatic polyvalent isocyanate compounds and the like; and isocyanate-terminated urethane prepolymers obtained by reacting the aromatic polyisocyanate compound and the like with a polyol compound.

The "adduct" is a reaction product of the aromatic polyisocyanate compound, the aliphatic polyisocyanate compound or the alicyclic polyisocyanate compound with a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, and examples thereof include a xylylene diisocyanate adduct of trimethylolpropane described later. The "isocyanate-terminated urethane prepolymer" refers to a prepolymer having a urethane bond and an isocyanate group at the terminal of the molecule.

More specifically, examples of the organic polyisocyanate compound include: 2, 4-toluene diisocyanate; 2, 6-toluene diisocyanate; 1, 3-xylylene diisocyanate; 1, 4-xylene diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; 3-methyl diphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4, 4' -diisocyanate; dicyclohexylmethane-2, 4' -diisocyanate; a compound obtained by adding one or more of tolylene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or part of the hydroxyl groups of a polyhydric alcohol such as trimethylolpropane; lysine diisocyanate, and the like.

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

When an organic polyisocyanate compound is used as the crosslinking agent (e), a hydroxyl group-containing polymer is preferably used as the energy ray-curable component (a) and/or the polymer (b). When the crosslinking agent (e) has an isocyanate group and the energy ray-curable component (a) and/or the polymer (b) has a hydroxyl group, a crosslinked structure can be easily introduced into the energy ray-curable resin layer (I) by the reaction of the crosslinking agent (e) with the energy ray-curable component (a) and/or the polymer (b).

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

[ thermosetting component (f) ]

Examples of the thermosetting component (f) include: epoxy thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, and the like, and among these resins, 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 (f 2).

Examples of the epoxy resin (f1) include those known in the art, such as: polyfunctional epoxy resins, bisphenol A diglycidyl ethers and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, phenylene skeleton epoxy resins, and other bifunctional or higher epoxy compounds.

The epoxy resins (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 a vinyl group (vinyl group), a 2-propenyl group (allyl group), (meth) acryloyl group, or (meth) acrylamide group can be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin having an unsaturated hydrocarbon group, the reliability of the resulting package is improved.

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

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

The thermosetting agent (f2) functions as a curing agent for the epoxy resin (f 1).

Examples of the thermosetting agent (f2) include: a compound having 2 or more functional groups capable of reacting with an epoxy group in 1 molecule. Examples of the functional group include: and a group obtained by forming an acid anhydride of a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, or an acid group, and the like, preferably a group obtained by forming an acid anhydride of a phenolic hydroxyl group, an amino group, or an acid group, and more preferably a phenolic hydroxyl group or an amino group.

The heat-curing agent (f2) may be used alone or in combination of two or more.

Among the thermosetting agents (f2), examples of the phenolic curing agent having a phenolic hydroxyl group include: multifunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, aralkyl phenol resins, and the like.

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

The content of the thermosetting agent (f2) is preferably 0.01 to 20 parts by mass per 100 parts by mass of the epoxy resin (f 1).

The content of the thermosetting component (f) (for example, the total content of the epoxy resin (f1) and the thermosetting agent (f 2)) is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the polymer (b).

[ curing Accelerator (g) ]

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

Preferred examples of the curing accelerator (g) include: tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylboron and triphenylphosphine tetraphenylboron.

When the curing accelerator (g) is used, the content of the curing accelerator (g) is preferably 0.01 to 10 parts by mass per 100 parts by mass of the thermosetting component (f).

[ general additive (z) ]

The general-purpose additive (z) may be any known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, and examples thereof include: filler, colorant, plasticizer, antistatic agent, antioxidant, getter, etc.

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

Examples of the filler include inorganic fillers and organic fillers, and the use of these fillers can adjust the thermal expansion coefficient of the cured resin layer (I').

The energy ray-curable resin layer (I) may or may not contain a filler, but when containing a filler, the content thereof is preferably 5 to 87% by mass, more preferably 7 to 78% by mass, 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), from the viewpoint of more effectively suppressing the occurrence of warpage.

Examples of the filler include: a filler material comprising a thermally conductive material.

Examples of the inorganic filler include: powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic filler materials; glass fibers, and the like.

The filler preferably has an average particle diameter of 0.01 to 20 μm, more preferably 0.1 to 15 μm, and further preferably 0.3 to 10 μm. When the average particle diameter of the filler is within the above range, the decrease in the 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 contain a colorant or may not contain a colorant, but when containing a colorant, the smaller the content thereof, the more preferable the content thereof is, and specifically, the content thereof is preferably less than 5% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass, relative to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I).

< method for producing energy ray-curable resin composition >)

The energy ray-curable resin composition can be obtained by blending the components constituting the composition.

The order of addition of the components in the mixing is not particularly limited, and two or more components may be added simultaneously.

In the case of using a solvent, the solvent may be used by mixing the solvent with any compounding ingredients other than the solvent and then diluting the compounding ingredients in advance, or the solvent may be used by mixing the solvent with the compounding ingredients without diluting any compounding ingredients other than the solvent in advance.

The method for mixing the components at the time of compounding is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a paddle, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.

The temperature and time for adding and mixing the components are not particularly limited as long as the components do not deteriorate, and may be appropriately adjusted, but the temperature is preferably 15 to 30 ℃.

Examples of the solvent include: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone. Among these solvents, methyl ethyl ketone, toluene, and ethyl acetate are preferable from the viewpoint of enabling the components contained in the energy ray-curable resin composition to be more uniformly mixed. The solvent may be used alone or in combination of two or more.

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

Examples of the energy ray-curable resin layer (I) composed of two or more layers include: an energy ray-curable resin layer (I) having an energy ray-curable resin layer (I-I) for imparting a cured resin layer (I ') having a high storage modulus E' and an energy ray-curable resin layer (I-ii) having a high adhesive force. In the case of such a configuration, by disposing the energy ray-curable resin layer (I-ii) on the surface on the side where the object to be sealed is placed, the object to be sealed can be strongly fixed, and the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I-I) can be effectively inhibited from warping after curing, so that the performance as a temporary fixing layer and the performance as a warp-preventing layer can be more highly satisfied. As for the preferable composition and physical properties of the energy ray-curable resin layers (I-I) and (I-ii), the composition and physical properties corresponding to the desired functions may be appropriately selected from the preferable composition and physical properties of the energy ray-curable resin layer (I) and used.

The thickness of the energy ray-curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, still more preferably 10 to 200 μm, yet more preferably 15 to 100 μm, and yet more preferably 20 to 50 μm. When the thickness of the energy ray-curable resin layer (I) is equal to or greater than the lower limit value, a cured sealing body in which warpage is more effectively suppressed can be obtained, and when the thickness is equal to or less than the upper limit value, an increase in cost can be suppressed, and excellent curability can be obtained.

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

The cured resin layer (I ') obtained by curing the energy ray-curable resin layer (I) preferably has a storage modulus E' of 1.0 × 10 at 23 ℃ from the viewpoint of obtaining a laminate capable of producing a cured sealant with a cured resin layer having a flat surface with suppressed warpage⁷Pa or more, more preferably 1.0X 10⁸Pa or more, more preferably 5.0X 10⁸Pa or more, more preferably 1.0X 10⁹The above is preferably 1.0 × 10¹³Pa or less, more preferably 1.0X 10¹²Pa or less, more preferably 5.0X 10¹¹Pa or less, more preferably 1.0X 10¹¹Pa or less.

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

< method for producing laminate >

The laminate according to one embodiment of the present invention can be produced, for example, by forming the pressure-sensitive adhesive layer (X), the substrate (Y), and the energy ray-curable resin layer (I) separately and bonding them to form a desired structure. The respective layers can be formed, for example, by applying a resin composition for forming the respective layers on a release material and drying the resin composition.

The method for producing the laminate according to one embodiment of the present invention is not limited to the above-described method, and for example, a method of forming a multilayer structure by applying a resin composition to a specific layer in order to form a layer, such as a method of applying a resin composition (Y) for forming a substrate (Y) to a pressure-sensitive adhesive layer (X) formed on a release material and further applying an energy ray-curable resin composition thereto, may be used. In this case, a plurality of layers may be simultaneously applied using, for example, a multilayer coater.

[ method for producing cured sealing Material ]

A method for producing a cured sealing body according to an embodiment of the present invention is a method for producing a cured sealing body using a laminate according to an 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 part of the surface of the energy ray-curable resin layer (I) of the laminate

Step (iii): a step of coating the object to be sealed and the surface of the cured resin layer (I') on at least the peripheral portion of the object to be sealed with a thermosetting sealing material, and thermosetting the sealing material to form a cured sealing body containing the object to be sealed

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

The cured sealing body according to an embodiment of the present invention is a sealing body obtained by coating an object to be sealed with a sealing material and curing the sealing material, and is composed of the object to be sealed and a cured product of the sealing material.

Fig. 4 is a schematic sectional view showing a step of producing a cured sealing body using the laminate 1a shown in fig. 1 (a). Hereinafter, the above-described steps will be described with reference to fig. 4 as appropriate.

< step (i) >

The step (I) is a step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) included in the laminate according to one embodiment of the present invention.

Fig. 4(a) shows a state in which the laminate 1a is used in this step, the adhesive surface of the pressure-sensitive adhesive layer (X) of the support layer (II) is bonded to the support 50, and the object to be sealed 60 is placed on a part of the surface of the energy ray-curable resin layer (I).

Fig. 4(a) shows an example in which the laminate 1a shown in fig. 1(a) is used, but when a laminate according to an embodiment of the present invention having another configuration is used, the support, the laminate, and the object to be sealed are similarly laminated or placed in this order.

The temperature condition in the step (i) is preferably a temperature at which the thermally expandable particles do not expand, and for example, is preferably performed in an environment of 0 to 80 ℃ (in the case where the expansion start temperature (t) is 60 to 80 ℃, the temperature condition is preferably performed in an environment lower than the expansion start temperature (t)).

The support is preferably affixed to the entire adhesive surface of the adhesive layer (X) of the laminate.

Therefore, the support is preferably plate-shaped. As shown in fig. 4, the surface area of the support to be bonded to the bonding surface of the pressure-sensitive adhesive layer (X) is preferably equal to or larger than the bonding surface area of the pressure-sensitive adhesive layer (X).

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

Specific examples of the material constituting the support include: metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastic, special engineering plastic, polyimide resin, polyamide-imide resin and other resin materials; and composite materials such as glass epoxy resins, and among these, SUS, glass, and silicon wafers are preferable. In addition, from the viewpoint of being able to irradiate the energy ray-curable resin layer (I) with an energy ray through the support, the support is preferably a transparent material such as glass.

The engineering plastics include: nylon, Polycarbonate (PC), and polyethylene terephthalate (PET).

As the special engineering plastics, there may be mentioned: polyphenylene Sulfide (PPS), polyether sulfone (PES), and polyether ether ketone (PEEK).

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

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

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

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

The semiconductor chip is preferably mounted such that the back surface of the semiconductor chip on the side opposite to the circuit surface is covered with the surface of the energy ray-curable resin layer (I). In this case, the circuit surface of the semiconductor chip is exposed after the mounting.

The semiconductor chip can be mounted using a known apparatus such as a flip chip bonder or a die bonder.

The layout, the number of semiconductor chips to be arranged, and the like may be determined as appropriate depending on the form, the number of products, and the like of the intended package.

Here, the laminate according to one embodiment of the present invention is preferably applied to a package in which a region larger than the chip size is covered with a sealing material for a semiconductor chip, such as FOWLP or FOPLP, so that a rewiring layer is formed not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material.

Therefore, the semiconductor chip is mounted on a part of the surface of the energy ray-curable resin layer (I), and preferably, the plurality of semiconductor chips are mounted on the surface in a state of being arranged with a constant interval therebetween, and more preferably, the plurality of semiconductor chips are mounted on the surface in a state of being arranged in a matrix form of a plurality of rows and a plurality of columns with a constant interval therebetween.

The interval between the semiconductor chips may be determined as appropriate according to the form of the intended package.

< step (ii) >

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

Fig. 4(b) shows a state where the energy ray-curable resin layer (I) is cured in this step to form a cured resin layer (I').

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

The illumination intensity of the energy ray during curing of the energy ray-curable resin layer (I) is preferably 4 to 280mW/cm²The amount of the energy ray during curing is preferably 5 to 1000mJ/cm²More preferably 100 to 500mJ/cm²。

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

The energy ray can be irradiated from any direction as long as it is a direction in which the energy ray-curable resin layer (I) can be irradiated with the energy ray, but by using a material having excellent light transmittance as the support (II) and the support 50, for example, the energy ray-curable resin layer (I) can be irradiated with the energy ray through the support 50, the adhesive layer (X), and the substrate (Y) while the support (II) and the support 50 are interposed therebetween (i.e., while being incident from the surface of the support 50 on the side opposite to the adhesive layer (X) in fig. 4 (b)).

< step (iii) >

The step (iii) is a step of forming a cured sealing body including the object to be sealed by coating the object to be sealed and the surface of the cured resin layer (I') on at least the peripheral portion of the object to be sealed with a thermosetting sealing material (hereinafter, also referred to as "coating treatment") and thermally curing the sealing material.

In the coating treatment, first, the object to be sealed and at least the peripheral portion of the surface of the cured resin layer (I') are coated with the sealing material.

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

For example, fig. 4(c) shows a state in which the object to be sealed 60 and the cured resin layer (I') are covered with the sealing material 70 so as to cover the entire surfaces thereof.

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

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

The sealing material may be in a solid state such as a granular state, a pellet state, a film state or the like at room temperature, or may be in a liquid state in the form of a composition, but from the viewpoint of workability, a sealing resin film as a film-shaped sealing material is preferable.

The coating method may be appropriately selected from conventional methods used in the sealing step depending on the type of the sealing material, and examples thereof include roll lamination, vacuum pressing, vacuum lamination, spin coating, die coating, transfer molding, and compression molding.

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

The heat curing treatment in the step (iii) is performed at a temperature at which the thermally expandable particles do not expand, and for example, when a laminate having a layer containing thermally expandable particles is used, it is preferably performed at a temperature lower than the expansion starting temperature (t) of the thermally expandable particles.

In the manufacturing method according to an embodiment of the present invention, as shown in fig. 4(c), the thermosetting treatment is performed in a state where the cured resin layer (I') is provided on the surface of the object to be sealed 60 sealed with the sealing material 70.

Since the cured resin layer (I') is provided, it is considered that the difference in shrinkage stress between the two surfaces of the obtained cured sealing body can be reduced, and the occurrence of warpage in the cured sealing body can be effectively suppressed.

< Process (iv) >

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

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

As shown in fig. 4(d), the cured sealing body with the cured resin layer 100 having the cured sealing body 80 obtained by sealing the object to be sealed 60 and the cured resin layer (I') can be obtained by separating the object to be sealed at the interface P.

The presence of the cured resin layer (I') has a function of effectively suppressing the occurrence of warpage in the cured sealing body, and also protects the object to be sealed, thereby contributing to improvement in reliability of the object to be sealed.

The "treatment of expanding" in the step (iv) is a treatment of expanding the thermally expandable particles by heating at a temperature not lower than the expansion starting temperature (t) of the thermally expandable particles, and by this treatment, irregularities are generated on the surface of the support layer (II) on the cured resin layer (I') side. As a result, the separation can be performed easily at the interface P with a small force at a time.

The "temperature not lower than the expansion start temperature (t)" when the thermally expandable particles are expanded is preferably not lower than the "expansion start temperature (t) +10 ℃ and not higher than the" expansion start temperature (t) +60 ℃, and more preferably not lower than the "expansion start temperature (t) +15 ℃ and not higher than the" expansion start temperature (t) +40 ℃ ".

The heating method is not particularly limited, and examples thereof include heating methods using a hot plate, an oven, a calciner, an infrared lamp, a hot air blower, and the like, and a method in which a heat source for heating can be preferably provided on the support 50 side from the viewpoint of easy separation at the interface P between the support layer (II) and the cured resin layer (I').

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

< first grinding step >

Fig. 5(a) shows the cured encapsulant 100 with the cured resin layer obtained by the above-described manufacturing method, and fig. 5(b) shows a first grinding step of grinding the surface 100a of the cured encapsulant 80 opposite to the cured resin layer (I') by a grinding mechanism 110 to expose the circuit surface 60a of the semiconductor chip 60.

The grinding mechanism 110 is not particularly limited, and may be performed using a known grinding device such as a grinding machine.

In the first grinding step, it is preferable that the surface of the cured sealing body on the cured resin layer (I') side is fixed to a separate support in advance from the viewpoint of workability.

In addition, from the viewpoint of workability, the cutting may be performed in a predetermined size including one or more chips before the first grinding step.

< Process for Forming redistribution layer and external terminal electrode >

Fig. 5(c) shows a rewiring layer and external terminal electrode forming step of forming a rewiring layer 200 and an external terminal electrode 300 electrically connected to the circuit surface 60a of the semiconductor chip 60 exposed on the surface of the cured sealing body 80 by the first grinding step.

The 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 may be formed by a known method such as a subtractive method or a semi-additive method, or 1 or more insulating layers may be provided as necessary.

The external terminal electrode 300 is electrically connected to the external electrode pad of the rewiring layer 200. The external electronic electrodes 300 may be formed by, for example, solder bonding of solder balls or the like.

< cutting step >

Fig. 5(d) shows a step of cutting the cured sealing body 100 with the cured resin layer to which the external terminal electrodes 300 are connected.

The dicing may be performed in 1 unit of the semiconductor chip, or may be performed in a given size including a plurality of semiconductor chips. The method for cutting the cured sealing body 100 with the cured resin layer is not particularly limited, and may be performed by a cutting mechanism such as a dicing saw.

< second grinding step >

Fig. 5(e) shows a second grinding step of grinding the cured resin layer (I') disposed on the side opposite to the redistribution layer 200 of the cured encapsulant 80 by the grinding mechanism 110. At this time, the surface of the cured sealing body 80 on the rewiring layer 200 side is preferably fixed in advance by a back-grinding tape or the like. The grinding mechanism 110 may be the same as that used in the first grinding step.

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

By grinding the cured resin layer (I'), further miniaturization of the resulting semiconductor package can be achieved. Therefore, from this viewpoint, it is preferable to grind the entire cured resin layer (I').

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

Examples

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

In the following description, the curable resin layer (I) represents both the "energy ray curable resin layer (I)" and the "thermosetting resin layer".

The physical property values in the examples are measured by the following methods.

< weight average molecular weight (Mw) >

The measurement was carried out under the following conditions using a gel permeation chromatography apparatus (product name "HLC-8020" available from Tosoh corporation) and the value was measured in terms of standard polystyrene.

(measurement conditions)

Column chromatography: a chromatographic column formed by sequentially connecting TSK guard column HXL-L, TSK gel G2500HXL, TSK gel G2000HXL and TSK gel G1000HXL (all manufactured by Tosoh Corp.) in sequence

Column temperature: 40 deg.C

Developing solvent: tetrahydrofuran (THF)

Flow rate: 1.0mL/min

< measurement of thickness of each layer >

The measurement was carried out using a constant-pressure thickness gauge (model: "PG-02J", Standard: based on JIS K6783, Z1702 and Z1709) manufactured by TECCLOCK.

< measurement method of expansion initiation temperature (t) and maximum expansion temperature of Heat-expansible particles >

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

A sample was prepared by placing 0.5mg of the thermally expandable particles to be measured in an aluminum cup having a diameter of 6.0mm (inner diameter: 5.65mm) and a depth of 4.8mm, and covering the aluminum cup with an aluminum lid (diameter: 5.6mm and thickness: 0.1mm) from above.

The height of the sample was measured using a dynamic viscoelasticity measuring apparatus in a state where a force of 0.01N was applied to the sample from the upper part of the aluminum cap by a indenter. Then, the sample was heated from 20 ℃ to 300 ℃ at a temperature rising rate of 10 ℃/min while a force of 0.01N was applied by the indenter, and the amount of displacement of the indenter in the vertical direction was measured, and the displacement start temperature in the positive direction was defined as the expansion start temperature (t).

The maximum expansion temperature is a temperature at which the displacement amount measured by the above method becomes maximum.

< evaluation of warpage >

The curable resin layer (I) of the curable resin layer (I) forming sheet prepared in each example was bonded 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 (product name "Epofix Resin" manufactured by Struers) and a curing agent (product name "Epofix hardner" manufactured by Struers) was prepared, and the Resin composition was applied to the surface of the silicon wafer opposite to the curable Resin layer (I) to a thickness of 30 μm. Thus, a pre-cured measurement sample having the curable resin layer (I)/silicon wafer/thermosetting resin composition layer in this order was obtained.

Next, when the curable resin layer (I) was an energy ray-curable resin layer (I), the resin layer was irradiated with ultraviolet rays using an ultraviolet irradiation apparatus RAD-2000 (manufactured by Linekec corporation) at an illuminance of 215mW/cm²Light quantity 187mJ/cm²The energy ray-curable resin layer (I) was cured by 3 times of ultraviolet irradiation under the conditions of (1) to form a cured resin layer (I'). In addition, when the curable resin layer (I) is a thermosetting resin layer (I), it is cured by heating at 180 ℃ for 60 minutes to form a cured resin layer (I'). Then, the thermosetting resin composition was cured by heating 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 was obtained.

After the cured measurement sample was placed on a horizontal table, visual observation was performed, and the presence or absence of warpage was evaluated based on the following criteria. In the measurement sample after curing, the "silicon wafer/thermosetting resin layer" portion corresponds to the structure of the cured sealing body obtained by sealing the semiconductor chip with the thermosetting resin, and therefore the performance as the warpage preventing layer of the cured resin layer (I') can be evaluated by this evaluation.

A: the warping amount is less than 3 mm.

B: the warping amount is more than 3mm and less than 15 mm.

C: the warping amount is more than 15 mm.

When the curable resin layer (I) was not applied and the silicon wafer/thermosetting resin layer was formed by the same procedure as described above, the warpage amount was 15 mm.

< evaluation of separability >

After a silicon wafer was bonded to the surface of the curable resin layer (I) of the laminate obtained in each example, the curable resin layer (I) was cured by energy ray or heat to form a cured resin layer (I'). Next, the expandable base material layer (Y1) was expanded by heat expansion treatment to separate the cured resin layer (I') from the support layer (II), and the separability was evaluated based on the following criteria. The curing conditions for the curable resin layer (I) and the thermal expansion treatment conditions for the support layer (II) produced in each example were the same as those described in examples 1 to 5 and reference example 1, which will be described later.

A: the cured resin layer (I') was separable and had good appearance and no residual paste.

B: the cured resin layer (I') was separable and had good appearance, but had residual paste in some portions.

C: the separation was impossible, or residual paste was present on the entire surface of the cured resin layer (I '), or the appearance of the cured resin layer (I') was poor.

< storage modulus E' of expandable base Material layer (Y1)

The expandable base material layer (Y1) having a thickness of 200 μm prepared for the measurement of the storage modulus E' was set to a size of 5mm in length by 30mm in width by 200 μm in thickness, and the material from which the release material was removed was used as a test sample.

The storage modulus E' of the test sample at a given temperature was measured using a dynamic viscoelasticity measuring apparatus (product name "DMAQ 800" manufactured by TA Instruments) under conditions of a test initiation temperature of 0 ℃, a test completion temperature of 300 ℃, a temperature rise rate of 3 ℃/min, a frequency of 11Hz, and an amplitude of 20 μm.

< shear storage modulus G' of adhesive layer 1 (X1) and adhesive layer 2 (X2) >

The 1 st adhesive layer (X1) and the 2 nd adhesive layer (X2) were cut into a circular shape having a diameter of 8mm, and then the release materials were removed and laminated to prepare a material having a thickness of 3mm as a test sample.

The shear storage modulus G' of the test sample at a given temperature was measured by a torsional shear method using a viscoelasticity measuring apparatus (manufactured by Anton Paar, Inc., under the apparatus name "MCR 300") under conditions of a test start temperature of 0 ℃, a test end temperature of 300 ℃, a temperature rise rate of 3 ℃/min, and a frequency of 1 Hz.

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

The curable resin layer (I) obtained in each example was cured to obtain a test piece,the storage modulus E 'of the formed cured resin layer (I') at 23 ℃ was measured using a dynamic viscoelasticity measuring apparatus (product name "DMAQ 800" manufactured by TAInstructions) under conditions of a test initiation temperature of 0 ℃, a test completion temperature of 300 ℃, a temperature rise rate of 3 ℃/min, a frequency of 11Hz, and an amplitude of 20 μm. In the case where the curable resin layer (I) was an energy ray-curable resin layer (I), the test piece was irradiated with ultraviolet ray using an ultraviolet irradiation device RAD-2000 (manufactured by Linekekec Co., Ltd.) at an illuminance of 215mW/cm²Light quantity 187mJ/cm²Under the conditions (2) above, a material obtained by curing the resin layer (I) by irradiation with ultraviolet light 3 times was used as a test piece, and in the case where the curable resin layer (I) was a thermosetting resin layer (I), a material obtained by curing the resin layer (I) by heating at 180 ℃ for 60 minutes was used as a test piece.

Synthesis example 1

(Synthesis of "acrylic urethane resin" for swellable base layer (Y1))

In a reaction vessel under nitrogen atmosphere, isophorone diisocyanate was mixed with 100 parts by mass of a polycarbonate diol (carbonate diol) having a weight average molecular weight of 1,000 to obtain an equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of the isophorone diisocyanate of 1/1, then 160 parts by mass of toluene was added, and the reaction was carried out at 80 ℃ for 6 hours or more under stirring under nitrogen atmosphere until the isocyanate group concentration reached the theoretical amount.

Subsequently, a solution prepared by diluting 1.44 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by mass of toluene was added, and the reaction was further carried out at 80 ℃ for 6 hours until the isocyanate groups at both ends disappeared, whereby a urethane prepolymer having a weight average molecular weight of 2.9 ten thousand was obtained.

Then, 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 parts by mass of 1-thioglycerol, and 50 parts by mass of toluene were charged into a reaction vessel under a nitrogen atmosphere, and the temperature was raised to 105 ℃ with stirring. Then, 2.2 parts by mass of a solution prepared by diluting a radical initiator (product name "ABN-E" manufactured by Nippon Kogyo Co., Ltd.) with 210 parts by mass of toluene was added dropwise to the reaction vessel over 4 hours while keeping the temperature at 105 ℃.

After completion of the dropwise addition, the reaction was carried out at 105 ℃ for 6 hours to obtain a solution of an acrylic urethane resin having a weight-average molecular weight of 10.5 ten thousand.

[ production of sheet for Forming supporting layer (II) ]

Production example 1

(support layer (II-A))

A sheet for forming the support layer (II-A) was produced in the following order (1-1) to (1-4).

Details of the material used in the formation of each layer are as follows.

< adhesive resin >

Acrylic copolymer (i): an acrylic copolymer having a structural unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2 EHA)/2-hydroxyethyl acrylate (HEA) at a mass ratio of 80.0/20.0 and having an Mw of 60 ten thousand.

Acrylic copolymer (ii): an acrylic copolymer having a constitutional unit derived from a raw material monomer composed of n-Butyl Acrylate (BA)/Methyl Methacrylate (MMA)/2-hydroxyethyl acrylate (HEA)/acrylic acid (mass ratio) of 86.0/8.0/5.0/1.0 and having an Mw of 60 ten thousand.

< additives >

Isocyanate crosslinking agent (i): the product was named "Coronate L" manufactured by Tosoh corporation, and had a solid content concentration of 75% by mass.

< thermally expandable particles >

Thermally expandable particles a: wuyu, Ltd, product name "S2640", expansion initiation temperature (t) of 208 ℃ and average particle diameter (D)₅₀) 24 μm, 90% particle size (D)₉₀)＝49μm。

< Release Material >

Heavy release film: a polyethylene terephthalate (PET) film having a release agent layer formed of a silicone-based release agent provided on one surface thereof and having a thickness of 38 μm, was manufactured by Lindelidae corporation under the trade name "SP-PET 382150".

Light release film: a film having a release agent layer formed of a silicone release agent provided on one surface of a PET film and having a thickness of 38 μm, manufactured by Lindelidae corporation and having a product name of "SP-PET 381031".

(1-1) formation of 1 st adhesive layer (X1)

An adhesive composition having a solid content (effective component concentration) of 25 mass% was prepared by adding 5.0 parts by mass of the isocyanate-based crosslinking agent (i) to 100 parts by mass of the solid content of the acrylic copolymer (i) as an adhesive resin, diluting with toluene, and stirring the mixture uniformly.

Then, the pressure-sensitive adhesive composition was applied to the surface of the release agent layer of the heavy release film (hereinafter also referred to as "release-treated surface") to form a coating film, and the coating film was dried at 100 ℃ for 60 seconds to form a1 st pressure-sensitive adhesive layer (X1) as a non-heat-expandable pressure-sensitive adhesive layer having a thickness of 5 μm.

The 1 st adhesive layer (X1) had a shear storage modulus G' (23) of 2.5X 10 at 23 ℃⁵Pa。

In addition, the adhesive force of the 1 st adhesive layer (X1) at 23 ℃ measured based on the above method was 0.3N/25 mm.

(1-2) formation of 2 nd adhesive layer (X2)

To 100 parts by mass of the solid content of the acrylic copolymer (ii) as an adhesive resin, 0.8 part by mass of the isocyanate-based crosslinking agent (i) was added, and the mixture was diluted with toluene and stirred uniformly to prepare an adhesive composition having a solid content (effective component concentration) of 25% by mass.

Then, the pressure-sensitive adhesive composition was applied to the release-treated surface of the light release film to form a coating film, and the coating film was dried at 100 ℃ for 60 seconds to form a2 nd pressure-sensitive adhesive layer (X2) having a thickness of 10 μm.

The 2 nd adhesive layer (X2) had a shear storage modulus G' (23) of 9.0X 10 at 23 ℃⁴Pa。

In addition, the adhesive force of the 2 nd adhesive layer (X2) at 23 ℃ measured based on the above method was 1.0N/25 mm.

(1-3) production 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 crosslinking agent (i), 1.4 parts by mass of tin dioctylbis (2-ethylhexanoate) as a catalyst, and the thermally expandable particles a were mixed, diluted with toluene, and stirred uniformly to prepare a resin composition having a solid content (effective component concentration) of 30% by mass.

The content of the thermally expandable particles a was 20 mass% based on the total amount (100 mass%) of the active ingredients in the obtained resin composition.

Then, the resin composition was applied to the surface of a polyethylene terephthalate (PET) film (product name: COSMOSHINE A4100, manufactured by Toyo chemical Co., Ltd., probe tack value: 0mN/5 mm. phi.) having a thickness of 50 μm as a non-swelling substrate to form a coating film, and the coating film was dried at 100 ℃ for 120 seconds to form a swelling substrate layer (Y1) having a thickness of 50 μm.

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

Thus, a substrate (Y) was prepared which was composed of an expandable substrate layer (Y1) having a thickness of 50 μm and a non-expandable substrate layer (Y2) having a thickness of 50 μm.

As a sample for measuring the storage modulus E' and the probe tack value of the expandable base layer (Y1), a coating film was formed by applying the resin composition to the release-treated surface of the light release film, and the coating film was dried at a gas atmosphere temperature of 100 ℃ for 120 seconds, thereby similarly forming an expandable base layer (Y1) having a thickness of 200 μm.

Then, the storage modulus and the probe tack value at each temperature of the expandable base material layer (Y1) were measured based on the above-mentioned measurement method, and the measurement results are shown below.

Storage modulus at 23 ℃ E' (23) ═ 2.0X 10⁸Pa

Storage modulus at 100 ℃ E' (100) ═ 3.0X 10⁶Pa

Storage modulus at 208 ℃ E' (208) ═ 5.0X 10⁵Pa

Viscosity value of probe 0mN/5mm phi

(1-4) lamination of layers

The non-expandable base material layer (Y2) of the base material (Y) produced in (1-3) above and the 2 nd pressure-sensitive adhesive layer (X2) formed in (1-2) above were bonded, and the expandable base material layer (Y1) and the 1 st pressure-sensitive adhesive layer (X1) formed in (1-1) above were bonded together.

Then, a support layer (II-a) forming sheet was produced in which the light release film/the 2 nd pressure-sensitive adhesive layer (X2)/the non-expandable base material layer (Y2)/the expandable base material layer (Y1)/the 1 st pressure-sensitive adhesive layer (X1)/the heavy release film were laminated in this order.

Production example 2

(support layer (II-B))

A support layer (II-B) forming sheet was produced in the same manner as in production example 1, except that in production example 1, the thermally expandable particles a were changed to the thermally expandable particles B described below, and the drying conditions after the resin composition was applied to form a coating film were changed to 100 ℃.

Thermally expandable particles B: manufactured by Japan Fillite corporation, trade name "031-40 DU", and expansion initiation temperature (t) of 80 ℃.

Production example 3

(support layer (II-C))

A support layer (II-C) forming sheet was produced in the same manner as in production example 1, except that in production example 1, the thermally expandable particles a were changed to the thermally expandable particles C described below, and the drying conditions after the resin composition was applied to form a coating film were changed to 100 ℃.

Thermally expandable particles C: manufactured by Japan Fillite corporation, product name "053-40 DU", expansion initiation temperature (t) 100 ℃.

In production examples 2 and 3, the drying temperature after the resin composition is applied to form a coating film is set to be higher than the expansion initiation temperature (t) of the thermally expandable particles when the sheet for forming the support layer (II) is formed, but since the drying temperature is a gas atmosphere temperature, no foaming is observed in the formed support layer (II).

Production example 4

(support layer (II-D))

A support layer (II-D) forming sheet was produced in the same manner as in production example 1, except that in production example 1, the thermally expandable particles a were changed to the thermally expandable particles D described below, and the drying conditions after the resin composition was applied to form a coating film were changed to 100 ℃.

Thermally expandable particles D: manufactured by Japan Fillite corporation, under the product name "920-40 DU", and the expansion initiation temperature (t) of 120 ℃.

[ production of sheet for Forming curable resin layer (I) ]

Production example 5

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

The following components were mixed in the respective kinds and amounts (all "effective component ratios") shown below, and then diluted with methyl ethyl ketone and stirred uniformly to prepare a solution of the curable composition having a solid content (effective component concentration) of 61 mass%.

[ (a2) component ]

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

[ (b) component ]

Acrylic polymer: an acrylic resin obtained by copolymerizing Butyl Acrylate (BA) (55 parts by mass), Methyl Acrylate (MA) (10 parts by mass), Glycidyl Methacrylate (GMA) (20 parts by mass) and 2-hydroxyethyl acrylate (HEA) (15 parts by mass) (glass transition temperature: -28 ℃, Mw:80 ten thousand): 17 parts by mass

[ (c) component ]

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

[ (d) component ]

An epoxy group-containing oligomer-type silane coupling agent (product name "MSEP 2" manufactured by Mitsubishi chemical corporation): 0.6 part by mass

[ (e) ingredient ]

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

[ (f) ingredient ]

Liquid bisphenol a-type epoxy resin (product name "BPA 328" manufactured by japan catalyst corporation): 16 parts by mass

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

Dicyclopentadiene type epoxy resin (product name "HP-7200 HH" available from DIC Co., Ltd.): 27 parts by mass

Dicyandiamide (product name "ADEKA HARDENER 3636 AS" available from ADEKA corporation): 1.5 parts by mass

[ (g) ingredient ]

Imidazole (product name "2 PH-Z" manufactured by Shikoku Kabushiki Kaisha): 1.5 parts by mass

The solution of the curable composition prepared above was applied to the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ℃ for 2 minutes to form an energy ray-curable resin layer (I-a) having a thickness of 25 μm, thereby producing an energy ray-curable resin layer (I-a) -forming sheet comprising the energy ray-curable resin layer (I-a) and the light release film.

Production example 6

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

[ (a2) component ]

ε -caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate (product name "A-9300-1 CL" manufactured by Ningmura chemical Co., Ltd., trifunctional ultraviolet-curable compound): 10 parts by mass

[ (b) component ]

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

[ (c) component ]

2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (product name "Irgacure (registered trademark) 369" manufactured by BASF Co.): 0.6 part by mass

[ (d) component ]

3-methacryloxypropyltrimethoxysilane (product name "KBM-503" available from shin-Etsu chemical Co., Ltd.): 0.4 part by mass

[ (h) ingredient ]

Silica filler (fused silica filler, average particle size 8 μm): 57 parts by mass

[ (z) component ]

A Pigment obtained by mixing 32 parts by mass of a phthalocyanine-based Blue Pigment (Pigment Blue 15:3), 18 parts by mass of an isoindoline-based Yellow Pigment (Pigment Yellow 139), and 50 parts by mass of an anthraquinone-based Red Pigment (Pigment Red 177) and pigmenting the mixture so that the total amount of the three pigments/the amount of the styrene acrylic resin is 1/3 (mass ratio): 4 parts by mass

The solution of the curable composition prepared above was applied to the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ℃ for 2 minutes to form an energy ray-curable resin layer (I-B) having a thickness of 25 μm, thereby producing an energy ray-curable resin layer (I-B) -forming sheet comprising the energy ray-curable resin layer (I-B) and the light release film.

Production example 7

(thermosetting resin layer (I-C))

Acrylic polymer: an acrylic resin obtained by copolymerizing Butyl Acrylate (BA) (1 part by mass), Methyl Acrylate (MA) (74 parts by mass), Glycidyl Methacrylate (GMA) (15 parts by mass) and 2-hydroxyethyl acrylate (HEA) (10 parts by mass) (glass transition temperature: 8 ℃, Mw:44 ten thousand): 18 parts by mass

Liquid bisphenol a-type epoxy resin (product name "BPA 328" manufactured by japan catalyst corporation): 3 parts by mass

Solid bisphenol a epoxy resin (product name "EPIKOTE 1055" manufactured by mitsubishi chemical corporation): 20 parts by mass

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

Dicyandiamide (product name "ADEKA HARDENER 3636 AS" available from ADEKA corporation): 0.5 part by mass

Imidazole (product name "2 PH-Z" manufactured by Shikoku Kabushiki Kaisha): 0.5 part by mass

An epoxy group-containing oligomer-type silane coupling agent (product name "MSEP 2" manufactured by Mitsubishi chemical corporation): 0.5 part by mass

Spherical silica filler (product name "SC 2050 MA" manufactured by Admatechs Co., Ltd.): 6 parts by mass

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

The solution of the curable composition prepared above was applied to the release-treated surface of the light release film to form a coating film, and the coating film was dried at 120 ℃ for 2 minutes to form a thermosetting resin layer (I-C) having a thickness of 25 μm, thereby producing a sheet for forming a thermosetting resin layer (I-C) comprising the thermosetting resin layer (I-C) and the light release film.

[ production of laminate ]

Examples 1 to 5, reference example 1

The heavy release film of the support layer (II) forming sheet shown in table 1 was removed, and the exposed 1 st pressure-sensitive adhesive layer (X1) was bonded to the surface of the curable resin layer (I) forming sheet shown in table 1, to obtain a laminate. In example 5, as the sheet for forming the support layer (II-E), a product name "revalph 3195" (expansion start temperature (t) ═ 170 ℃) manufactured by hitong electric corporation was used.

The results of evaluation of the separability and warpage of the laminate obtained in each example are shown in table 1.

[ production of cured sealing Material ]

Next, using the laminate obtained in each example, a cured sealing body was produced in the following procedure.

(1) Mounting of semiconductor chips

The light release film on the support layer (II) side of the laminate was removed, and the exposed adhesive surface of the 2 nd pressure-sensitive adhesive layer (X2) of the support layer (II) was bonded to the support (glass).

Then, the light release film on the curable resin layer (I) side was also removed, and 9 semiconductor chips (each having a chip size of 6.4mm × 6.4mm and a chip thickness of 200 μm (#2000)) were mounted on the exposed surface of the curable resin layer (I) with a necessary interval so that the back surface of each semiconductor chip on the opposite side to the circuit surface was in contact with the surface of the curable resin layer (I).

(2) Formation of the cured resin layer (I')

In examples 1 to 5, after the above (1) and before the following (3), the energy ray curable resin layer (I) as the curable resin layer (I) was irradiated with ultraviolet rays (UV) to form a cured resin layer (I') on which the semiconductor chip was mounted. Incidentally, the irradiation intensity was 215mW/cm from the support (glass) side using an ultraviolet irradiation apparatus RAD-2000 (manufactured by Lindco Co., Ltd.)²Light quantity 187mJ/cm²The conditions of (3) were subjected to ultraviolet irradiation.

In reference example 1, (2) was not performed, and in (3) described later, the thermosetting resin layer as the curable resin layer (I) was simultaneously cured in the process of curing the sealing material.

(3) Formation of cured seal

The surfaces of 9 semiconductor chips and the cured resin layer (I') at least at the peripheral portion of the semiconductor chips (thermosetting resin layer in reference example 1) were coated with a thermosetting sealing resin film as a sealing material, and the sealing resin film was thermally cured using a vacuum heat and pressure laminator (product name "7024 HP 5" manufactured by ROHM and HAAS corporation) to prepare a cured sealing body. The sealing conditions were as follows.

Preheating temperature: the working table and the diaphragm (diaphragm) are both 100 DEG C

Vacuum suction: 60 seconds

Dynamic pressurization mode: 30 seconds

Static pressurization mode: 10 seconds

Sealing temperature: 60 minutes at 180 DEG C

(4) Separation at the interface P

After the above (3), the thermal expansion treatment was performed for 3 minutes at the expansion start temperature (t) +30 ℃ of the thermal expandable particles contained in the support layer (II) of each laminate, and the separation was performed at the interface P between the 1 st pressure-sensitive adhesive layer (X1) of the support layer (II) and the cured resin layer (I'). Thereby, a cured sealing body with a cured resin layer was obtained.

[ Table 1]

As is clear from table 1, in examples 1 to 5 using the laminate according to one embodiment of the present invention, the formed cured sealing body was not warped and the separation property of the support layer (II) was excellent.

On the other hand, in reference example 1 in which a thermosetting resin layer was used as the curable resin layer, the support layer (II) could not be separated from the cured resin layer (I').

Claims

1. A laminate, comprising:

an energy ray-curable resin layer (I), and

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

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

the cured resin layer (I') obtained by curing the energy ray-curable resin layer (I) and the support layer (II) are separated at the interface by a treatment of expanding the thermally expandable particles.

2. The laminate according to claim 1, wherein the cured resin layer (I ') obtained by curing the energy ray-curable resin layer (I) has a storage modulus E' of 1.0X 10 at 23 ℃⁷～1.0×10¹³Pa。

3. The laminate according to claim 1 or 2, wherein the thickness of the energy ray-curable resin layer (I) is 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.

5. 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 adhesive layer (X) is a non-expandable adhesive layer.

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

8. The laminate according to any one of claims 5 to 7,

9. The laminate according to any one of claims 1 to 8, which is used for forming a cured seal containing an object to be sealed, as follows:

after the sealing material is thermally cured, the cured resin layer (I') and the support layer (II) are separated at the interface by a process of expanding the thermally expandable particles, thereby forming a cured sealing body including the object to be sealed.

10. The laminate according to claim 9, for preventing warpage of the cured seal.

11. A method for producing a cured sealing body by using the laminate according to any one of claims 1 to 10, comprising the following steps (i) to (iv),

step (ii): a step of irradiating the energy ray-curable resin layer (I) with an energy ray to form a cured resin layer (I') obtained by curing the energy ray-curable resin layer (I);

step (iv): and a step of separating the cured resin layer (I') and the support layer (II) at the interface thereof by a treatment of expanding the thermally expandable particles to obtain a cured sealing body with a cured resin layer.