CN111886309A - Laminated body for warpage prevention of cured sealing body, and manufacturing method of cured sealing body - Google Patents

Abstract

The invention relates to a laminate for preventing warpage of a cured sealing body, which comprises a thermosetting resinA curable resin layer (I) of the curable resin layer (X1) and a support layer (II) supporting the curable resin layer (I), wherein the curable resin layer (I) has an adhesive surface having adhesiveness, the support layer (II) has a substrate (Y) and an adhesive layer (V), at least one of the substrate (Y) and the adhesive layer (V) contains thermally expandable particles, the curable resin layer (I), the adhesive layer (V), and the substrate (Y) are arranged in this order in the anti-warping laminate, and the adhesive surface of the curable resin layer (I) and the adhesive layer (V) are arranged on the opposite side, and the curing of the curable resin layer (I) is completed within 2 hours and the cured resin layer (I') is formed at a minimum curing temperature (T) of 2 hours or less₁) Is lower than the foaming initiation temperature (T) of the thermally expandable particles₂) The cured sealing body is produced by sealing an object to be sealed on the adhesive surface of the curable resin layer (I).

Description

Laminated body for warpage prevention of cured sealing body, and manufacturing method of cured sealing body

technical field

The present invention relates to a laminate for preventing warpage of a cured sealing body, and a method for producing the cured sealing body.

Background technique

In recent years, the miniaturization, weight reduction, and high functionality of electronic equipment have progressed, and a semiconductor chip may be mounted on a package whose size is close to that. Such packages are sometimes referred to as CSPs (Chip Scale Packages). Examples of CSP include: WLP (Wafer Level Package, wafer-level packaging) that processes the wafer size to the final packaging process and completes packaging, and PLP (Panel Level Package) that processes the panel size larger than the wafer size to the final packaging process and completes packaging. Package, panel level package), etc.

WLP and PLP are divided into fan-in (Fan-In) type and fan-out (Fan-Out) type. In the fan-out WLP (hereinafter also referred to as "FOWLP") and PLP (hereinafter also referred to as "FOPLP"), the semiconductor chip is covered with a sealing material to make a region larger than the chip size, and the curing of the semiconductor chip is formed The sealing body can form rewiring layers and external electrodes not only on the circuit surface of the semiconductor chip but also on the surface region of the sealing material.

FOWLP and FOPLP can be produced, for example, through the following steps: a placing step of placing a plurality of semiconductor chips on a sheet for temporary fixing; a covering step of covering with a thermosetting sealing material; and thermally curing the sealing material to obtain A curing step of curing the sealing body; a separation step of separating the cured sealing body from the sheet for temporary fixing; and a rewiring layer forming step of forming a rewiring layer on the surface of the exposed semiconductor chip side (hereinafter, also referred to in the cladding step and the processing performed in the curing process is called "sealing processing").

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

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2001-131507

SUMMARY OF THE INVENTION

Invention to solve problem

However, the inventors of the present invention have found that when a cured sealing body is produced using the pressure-sensitive adhesive sheet described in Patent Document 1 as a sheet for temporary fixing, when the heat-expandable particles are foamed by heating the temporary fixing layer , there is a possibility that the temporary fixing layer cannot be peeled off from the cured resin layer formed by the first-stage heating before the heating and foaming, and this problem tends to become prominent as the package size of FOWLP, FOPLP, etc. increases. .

In the cured sealing body in which peeling failure has occurred, not only the sealing object itself such as a semiconductor chip may be damaged, but also a part of the thermally expandable adhesive layer may remain on the cured resin layer, or the cured resin layer itself may be damaged. If it is damaged, it causes such a disadvantage that the process such as grinding and cutting of the cured sealing body scheduled in the subsequent process cannot be performed accurately.

In view of the above-mentioned problems, the present invention has an object to provide a laminate for warpage prevention having a support layer and a curable resin layer, and a method for producing a cured sealing body using the laminate for warpage prevention , it is possible to fix the object to be sealed on the surface of the curable resin layer to carry out the sealing process, and at the same time, it is possible to provide a cured resin layer as a warpage preventing layer to the cured sealing body formed by the sealing process, and to prevent the occurrence of curing The peeling of the resin layer and the support layer was poor.

way of solving the problem

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, as a result, they have found that the above-mentioned problems can be solved by setting the adhesive force of the curable resin layer within a predetermined range, and have completed the present invention.

That is, the present invention provides the following [1] to [10].

[1] A laminate for preventing warpage of a cured sealing body, comprising: a curable resin layer (I) including a thermosetting resin layer (X1), and a support layer (II) for supporting the curable resin layer (I) ,

The curable resin layer (I) has an adhesive surface, and the adhesive surface has adhesiveness,

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

The curable resin layer (I), the adhesive layer (V) and the base material (Y) are arranged in this order in the laminate for preventing warpage, and the above-mentioned adhesive surface of the curable resin layer (I) is bonded to the The agent layer (V) is arranged on the opposite side,

The minimum curing temperature (T ₁ ) at which the curing of the curable resin layer (I) is completed within 2 hours and the cured resin layer (I′) is formed is lower than the foaming initiation temperature (T ₂ ) of the above-mentioned thermally expandable particles temperature,

The said cured sealing body is manufactured by sealing the object to be sealed on the said adhesive surface of the curable resin layer (I).

[2] The laminate for preventing warpage according to the above [1], wherein the minimum curing temperature (T ₁ ) of the curable resin layer (I) and the foaming initiation temperature (T ₂ ) of the heat-expandable particles The difference (T ₂ -T ₁ ) is 20°C to 100°C.

[3] The laminate for preventing warpage according to the above [1] or [2], wherein the curable resin layer (I) has two or more thermosetting resin layers (X1), and the two or more thermosetting resin layers The minimum value (T _1a ) of the curing minimum temperature (T ₁ ) in (X1) is a temperature lower than the foaming initiation temperature (T ₂ ) of the thermally expandable particles.

[4] The laminate according to any one of the above [1] to [3], wherein the thermosetting resin layer (X1) has a thickness of 1 to 500 μm.

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

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

[7] The laminate according to the above [5] or [6], wherein the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1),

The support layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (V) in this order.

[8] The laminate for preventing warpage according to any one of the above [1] to [7], wherein the curable resin layer (I) has a first layer disposed on the side of the support layer (II), and an arrangement of The second layer on the above-mentioned adhesive surface side,

The above-mentioned first layer is a thermosetting resin layer (X1-1),

The said 2nd layer is an energy ray-curable resin layer (X2).

[9] A method for producing a cured sealing body using the laminate for preventing warpage according to any one of the above [1] to [7], the method comprising:

A step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) included in the above-mentioned warpage preventing laminate;

A step of covering the above-mentioned object to be sealed and the above-mentioned adhesive surface of the curable resin layer (I) in at least a peripheral portion of the above-mentioned object to be sealed with a thermosetting sealing material; and

The step of thermally curing the sealing material to form a cured sealing body including the object to be sealed, and simultaneously thermally curing the curable resin layer (I) to form a cured resin layer to obtain a cured sealing body with a cured resin layer .

[10] A method for producing a cured sealing body with a cured resin layer, comprising:

A step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) included in the above-mentioned warpage preventing laminate;

A step of curing the energy-ray-curable resin layer (X2) by irradiating energy rays;

A step of covering the above-mentioned object to be sealed and the above-mentioned adhesive surface of the curable resin layer (I) in at least a peripheral portion of the above-mentioned object to be sealed with a thermosetting sealing material; and

The above-mentioned sealing material is thermally cured to form a cured sealing body containing the above-mentioned sealing object, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I'), thereby obtaining curing with a cured resin layer. Process of sealing body.

effect of invention

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the cured sealing body using the laminated body for warping prevention which can fix the sealing object to the said curable resin and the laminated body for warping prevention can be provided While sealing the surface of the layer, a cured resin layer as a warpage preventing layer can be provided to the cured sealing body formed by the sealing, and the occurrence of poor peeling between the curable resin layer and the support layer can be prevented.

Description of drawings

[ Fig. 1] Fig. 1 is a schematic cross-sectional view of the laminate showing the configuration of the warpage preventing laminate according to the first embodiment of the present invention.

[ Fig. 2] Fig. 2 is a schematic cross-sectional view of the laminate showing the configuration of the warpage preventing laminate according to the second embodiment of the present invention.

[ Fig. 3] Fig. 3 is a schematic cross-sectional view of the laminate showing the configuration of the warpage preventing laminate according to the third embodiment of the present invention.

[ Fig. 4] Fig. 4 is a schematic cross-sectional view of the laminate showing the configuration of the warp preventing laminate according to the fourth embodiment of the present invention.

[ Fig. 5] Fig. 5 is a schematic cross-sectional view of the laminate showing the configuration of the warpage preventing laminate according to the fifth embodiment of the present invention.

[ Fig. 6] Fig. 6 is a schematic cross-sectional view showing a step of manufacturing a cured sealing body with a cured resin layer.

[ Fig. 7] Fig. 7 is a schematic cross-sectional view showing another manufacturing process of the cured sealing body with a cured resin layer.

Symbol Description

(I): Curable resin layer

(I'): Cured resin layer

(I ^* ): Curable resin layer after partial curing

(II): Support layer

(II’): Support layer after expansion

(V): Adhesive layer

(V1): (1st) Adhesive layer

(V1-1): 1st pressure-sensitive adhesive layer

(V2), (V1-2): Second pressure-sensitive adhesive layer

(X1), (X1-1), (X1-2): Thermosetting resin layer

(X1'): Thermosetting resin layer after curing

(X1-1'): Cured thermosetting resin layer

(X2): Energy ray-curable resin layer

(X2'): Energy ray-curable resin layer after curing

(Y): Substrate

(Y1): Intumescent base material layer

(Y1'): Expandable base material layer after expansion

(Y2): Non-expandable base material layer

1a, 1b, 2a, 2b, 3, 4, 5: Laminates for warpage prevention

50: Support body

60: Object to be sealed (semiconductor chip)

70: Forming mold

71: Injection hole

72: Molding space

80: Sealing material

81: Cured sealing material

85: Curing Seal

200: Cured sealing body with cured resin layer

P: interface

Detailed ways

First, the terms used in this specification will be described.

In the present specification, whether or not the target layer is a "non-expandable layer" can be determined as follows: after performing the treatment for swelling for 3 minutes, the volume change rate before and after the treatment calculated by the following formula is less than 5% In the case of , the layer is judged as a "non-expandable layer". On the other hand, when the said volume change rate is 5 % or more, this layer is judged as "expandable layer".

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

In addition, as "treatment for expanding", for example, in the case of a layer containing heat-expandable particles, the heat-treatment is performed at the expansion start temperature (t) of the heat-expandable particles for 3 minutes, that is, Can. In addition, when the expandable particle is a particle which expands by foaming, the said expansion start temperature (t) may be called foaming start temperature (T2 ₎ .

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

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

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

In this specification, regarding the preferable numerical range (for example, the range of content etc.), the lower limit value and upper limit value described in each segment can be combined independently. For example, according to the description of "preferably 10 to 90, more preferably 30 to 60", "preferable lower limit value (10)" and "more preferred upper limit value (60)" can also be obtained by combining "10 to 60".

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

In the present specification, "energy ray curability" means the property of curing by irradiation with energy rays, and "non-energy ray curability" means the property of not curing even when irradiated with energy rays.

In this specification, the minimum temperature which can complete the hardening of curable resin within 2 hours may be called "hardening minimum temperature."

In this specification, "curing is completed" means that the peak attributed to the curing reaction disappears from the temperature characteristic curve when a sample is measured using a differential scanning calorimetry analyzer.

Hereinafter, an embodiment of the present invention (hereinafter, may also be referred to as "this embodiment") will be described.

[Laminated body for warpage prevention]

The laminated body for warpage prevention which concerns on one Embodiment of this invention has a curable resin layer (I) containing a thermosetting resin layer (X1), and a support layer (II) which supports the curable resin layer (I). In addition, in the following description, the laminated body for warpage prevention may be abbreviated as "laminated body" in some cases.

The thermosetting resin layer (X1) is preferably directly laminated on the support layer (II).

The curable resin layer (I) has an adhesive surface, and the adhesive surface has adhesiveness.

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

The curable resin layer (I), the adhesive layer (V) and the base material (Y) are arranged in this order, and the above-mentioned bonding surface of the curable resin layer (I) and the adhesive layer (V) are arranged on the opposite side.

The minimum curing temperature (T ₁ ) at which the curing of the curable resin layer (I) is completed within 2 hours and the cured resin layer (I′) is formed is lower than the foaming initiation temperature (T ₂ ) of the above-mentioned thermally expandable particles temperature.

<Configuration of the laminate for warpage prevention>

The configuration of the warpage preventing laminate of the present embodiment will be described with reference to the drawings.

FIGS. 1 to 5 are schematic cross-sectional views of the laminates showing the configuration of the warpage preventing laminates according to the first to fifth embodiments of the present invention. In addition, in the laminated bodies of the following first to fifth embodiments, from the viewpoint of protecting the surfaces of the curable resin layer (I) and the support layer (II), etc., it is also possible to provide the laminates on the The adhesive surface of the adhesive layer (V1) of the support (not shown) and the first surface (the surface on the opposite side to the support layer (II)) of the curable resin layer (I) are further laminated with a release material. constitute. In addition, this peeling material can be peeled and removed when using the laminated body for warpage prevention.

[Laminated body for warpage prevention according to the first embodiment]

As a laminated body for warpage prevention of the 1st Embodiment of this invention, the laminated body 1a, 1b shown in FIG. 1 is mentioned.

Laminated bodies 1a and 1b have a structure including a support layer (II) having a base material (Y) and an adhesive layer (V1), and a curable resin layer (I), and the base material (Y) and curable The resin layers (I) are directly laminated together.

In the following description, the surface on the opposite side to the support layer (II) of the curable resin layer (I) may be referred to as a "first surface", and the surface on the support layer (II) side may be referred to as a "second surface". ".

The first surface of the curable resin layer (I) is an adhesive surface having a predetermined adhesive force, and when the object to be sealed is placed, the object to be sealed can be fixed by its adhesive force.

In addition, in the laminated bodies 1a and 1b, the adhesive surface of the adhesive layer (V1) is stuck to the support body which is not shown in figure.

The support layer (II) contains thermally expandable particles in at least any one of the base material (Y) and the pressure-sensitive adhesive layer (V1), and has expandability. In the laminated body 1a of Fig.1 (a), a base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles.

The base material (Y) may be a base material of a single-layer structure composed of only the intumescent base material layer (Y1) like the laminate 1a shown in Fig. 1(a), or may be a base material as shown in Fig. 1(b) A base material having a multilayer structure of an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) like the illustrated laminate 1b.

In addition, when using the base material (Y) which has an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) in the laminated body for warpage prevention of 1st Embodiment, it is preferable As shown in FIG. 1( b ), a non-expandable base material layer (Y2) is laminated on the surface of the pressure-sensitive adhesive layer (V1), and an expandable base material layer (Y2) is further laminated on the surface of the non-expandable base material layer (Y2). The structure of the base material layer (Y1).

In the laminated body 1a shown in Fig. 1(a), the thermally expandable particles contained in the expandable base material layer (Y1) expand by expansion treatment by heating (hereinafter, referred to as "heat expansion treatment"). Concavities and convexities are generated on the surface of the base material (Y), and the contact area with the cured resin layer obtained by curing the curable resin layer (I) decreases. In addition, in the following description, the layer obtained by hardening a curable resin layer is called a cured resin layer (I').

At this time, the adhesive surface of the adhesive layer (V1) is attached to a support (not shown). By sticking the pressure-sensitive adhesive layer (V1) to the support in a sufficiently close contact manner, even if a force causing unevenness is generated on the surface of the intumescent base material layer (Y1) on the pressure-sensitive adhesive layer (V1) side, Repulsive force with respect to the adhesive layer (V1) is also easily generated. Therefore, unevenness is less likely to be formed on the surface of the base material (Y) on the adhesive layer (V1) side.

As a result, in the laminated body 1a, the interface P of the base material (Y) of the support layer (II) and the cured resin layer (I') can be separated at one time and easily with a small force.

In addition, by forming the pressure-sensitive adhesive layer (V1) which the laminated body 1a has by using the pressure-sensitive adhesive composition which can increase the adhesive force with respect to the support body, it can also be carried out at the interface P more easily. separation. In the following description, the interface of the curable resin layer (I) and the support layer (II) may also be referred to as "interface P".

In addition, from the viewpoint of suppressing transmission of the stress caused by the thermally expandable particles to the pressure-sensitive adhesive layer (V1) side, it is preferable that the base material (Y) has a laminated body 1b as shown in Fig. 1(b) . Intumescent base material layer (Y1) and non-expandable base material layer (Y2).

Since the stress caused by the expansion of the thermally expandable particles in the expandable base material layer (Y1) is suppressed by the non-expandable base material layer (Y2), it is not easily transmitted to the pressure-sensitive adhesive layer (V1).

Therefore, unevenness is less likely to occur on the surface of the adhesive layer (V1) on the support side, the adhesiveness between the adhesive layer (V1) and the support is hardly changed before and after the heat expansion treatment, and good adhesion can be maintained sex. As a result, irregularities are easily formed on the surface of the intumescent base material layer (Y1) on the side of the curable resin layer (I), and as a result, the intumescent base material layer (Y1) and the cured resin layer ( The interface P of I') can be separated once and easily with little force.

In addition, it is preferable that the intumescent base material layer (Y1) and the curable resin layer (I) are directly laminated, as in the laminated body 1b shown in FIG. 1(b), and the non-expandable base material layer (Y2) ) in which the pressure-sensitive adhesive layer (V1) is laminated on the surface opposite to the curable resin layer (I).

Moreover, between the expandable base material layer (Y1) and the non-expandable base material layer (Y2), an adhesive layer and an anchor layer for bonding both may be provided, or they may be directly laminated.

[Laminated body for warpage prevention according to the second embodiment]

As a laminated body for warpage prevention of the 2nd Embodiment of this invention, the laminated bodies 2a and 2b for warpage prevention shown in FIG. 2 are mentioned.

The laminates 2a and 2b have a configuration in which the pressure-sensitive adhesive layer included in the support layer (II) has a first pressure-sensitive adhesive layer (V1-1) and a second pressure-sensitive adhesive layer (V1-2), and uses the first pressure-sensitive adhesive layer (V1-2). The adhesive layer (V1-1) and the second adhesive layer (V1-2) sandwich the substrate (Y), and the adhesive surface of the second adhesive layer (V1-2) and the curable resin layer ( I) Directly layered together. Hereinafter, each pressure-sensitive adhesive layer when the support layer (II) is provided with a plurality of pressure-sensitive adhesive layers and the pressure-sensitive adhesive layer when the support layer (II) is provided with a single pressure-sensitive adhesive layer may be collectively referred to as adhesives. Mixture layer (V).

In addition, in the laminated body for warpage prevention of this 2nd Embodiment, the adhesive surface of the 1st pressure-sensitive adhesive layer (V1-1) is stuck to the support body which is not shown in figure.

Also in the laminated body for warpage prevention of this 2nd Embodiment, it is preferable that a base material (Y) has an expandable base material layer (Y1) containing a heat-expandable particle.

The base material (Y) may be a base material of a single-layer structure composed of only the intumescent base material layer (Y1) like the laminate 2a shown in Fig. 2(a), or may be a base material as shown in Fig. 2(b) A base material having a multilayer structure of an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) like the illustrated laminate 2b.

However, as described above, from the viewpoint of forming a laminate that can keep the adhesiveness between the first pressure-sensitive adhesive layer (V1-1) and the support favorable before and after the thermal expansion treatment, it is preferable as shown in FIG. 2( b ). Specifically, the substrate (Y) is provided with an intumescent substrate layer (Y1) and a non-intumescent substrate layer (Y2).

In addition, when using the base material (Y) which has an intumescent base material layer (Y1) and a non-expandable base material layer (Y2) in the laminated body for warpage prevention of 2nd Embodiment, it is preferable As shown in FIG. 2( b ), the second pressure-sensitive adhesive layer (V1-2) is laminated on the surface of the intumescent base material layer (Y1), and the second pressure-sensitive adhesive layer (V1-2) is laminated on the surface of the non-expandable base material layer (Y2). There is a configuration of the first pressure-sensitive adhesive layer (V1-1).

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, so that the heat-expandable particles in the expandable base material layer (Y1) are expanded. The surface is uneven.

Furthermore, the second pressure-sensitive adhesive layer (V1-2) is pushed up by the unevenness generated on the surface of the intumescent base material layer (Y1), and the adhesion of the second pressure-sensitive adhesive layer (V1-2) Since unevenness is also formed on the surface, the contact area between the second pressure-sensitive adhesive layer (V1-2) and the cured resin layer (I') is reduced. As a result, the interface P between the second pressure-sensitive adhesive layer (V1-2) of the support layer (II) and the cured resin layer (I') can be separated at one time and easily with a small force.

In addition, in the laminated body of the present second embodiment, from the viewpoint of obtaining a laminated body which can be separated at one time and easily with a smaller force at the interface P, it is preferable that the support layer (II) has The structure in which the expandable base material layer (Y1) and the 2nd pressure-sensitive adhesive layer (V1-2) of the base material (Y) provided are directly laminated.

[Laminated body for warpage prevention according to the third embodiment]

As a laminated body for warpage prevention of the 3rd Embodiment of this invention, the laminated body 3 for warpage prevention shown in FIG. 3 is mentioned.

The laminate 3 shown in FIG. 3 has a structure including a support layer (II) having a first non-expandable pressure-sensitive adhesive layer on the surface side of the base (Y) side. 1 pressure-sensitive adhesive layer (V1), a second pressure-sensitive adhesive layer (V2) having an expandable pressure-sensitive adhesive layer containing heat-expandable particles on the surface side of the other side of the base material (Y), and a second pressure-sensitive adhesive layer (V2) The adhesive layer (V2) and the curable resin layer (I) are directly laminated together.

In the laminated body 3, the adhesive surface of the 1st pressure-sensitive adhesive layer (V1) is stuck to the support body which is not shown in figure.

In addition, it is preferable that the base material (Y) which the laminated body 3 of this 3rd Embodiment has is comprised by the non-expandable base material layer (Y2).

In the laminate 3 of the third embodiment, the thermally expandable particles in the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer, are expanded by the thermal expansion treatment, and the second pressure-sensitive adhesive The surface of the layer (V2) was uneven, and the contact area between the second pressure-sensitive adhesive layer (V2) and the curable resin layer (I) decreased.

On the other hand, since the surface on the side of the base material (Y) of the first pressure-sensitive adhesive layer (V1) is laminated on the base material (Y), unevenness is less likely to occur.

Therefore, it is easy to form unevenness on the surface of the second pressure-sensitive adhesive layer (V2) on the side of the curable resin layer (I) by the thermal expansion treatment, and as a result, the second pressure-sensitive adhesive layer (V2) of the support layer (II) ) and the interface P of the cured resin layer (I') can be separated at one time and easily with a small force.

[Laminated body for warpage prevention according to the fourth embodiment]

As a laminated body for warpage prevention of the 4th Embodiment of this invention, the laminated body 4 for warpage prevention shown in FIG. 4 is mentioned.

The laminate 4 shown in FIG. 4 has a structure in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are laminated in this order.

In the laminate 4, the curable resin layer (I) is composed of a first thermosetting resin layer (X1-1) located on the side of the base material (Y) and a second thermosetting resin layer located on the opposite side of the base material (Y). The curable resin layer (I) of (X1-2) is constituted. Both the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2) are non-expandable.

Here, the adhesive force on the surface of the second thermosetting resin layer (X1-2) is higher than that of the first thermosetting resin layer (X1-1). In the laminated body 4, by configuring the curable resin layer (I) with two thermosetting resin layers, layers having mutually different properties can be used. For example, the curable resin layer on the opposite side to the support layer (II) can be selected from a thermosetting resin layer containing a composition with higher adhesiveness, and the curable resin layer on the support layer (II) side can be selected from the support layer (II). ) with better separation properties.

[Laminated body for warpage prevention according to the fifth embodiment]

As the laminated body for warpage prevention according to the fifth embodiment of the present invention, the laminated body for warpage prevention 5 shown in FIG. 5 can be mentioned.

The laminate 5 shown in FIG. 5 has a structure in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are laminated in this order.

In the laminate 5, the curable resin layer (I) is composed of a thermosetting resin layer (X1-1) located on the side of the base material (Y) and an energy ray-curable resin layer (X1-1) located on the opposite side of the base material (Y). The curable resin layer (I) of X2) is constituted. Both the first thermosetting resin layer (X1-1) and the energy ray-curable resin layer (X2) are non-expandable.

In the laminated body 5, by dividing the curable resin layer (I) into an energy ray-curable resin layer (X2) and a thermosetting resin layer (X1-1), layers having mutually different properties can be used. For example, an energy-curable resin layer made of an energy ray-curable composition that can be easily adjusted to have a high adhesive force may be disposed on the opposite side of the support layer (II), and a sealant described later may be disposed on the support layer (II) side. A thermosetting resin layer with better material separation.

[Application of the laminate for warpage prevention]

The laminate for preventing warpage of the present embodiment can be used for the manufacture of a cured sealing body in which a sealing object is placed on the surface of a curable resin layer, and the sealing object and at least a peripheral portion of the sealing object are The surface of the thermosetting resin layer is covered with a sealing material, and the sealing material is cured to obtain a cured sealing body containing an object to be sealed.

In addition, the specific embodiment about manufacture of the cured sealing body using the laminated body for warpage prevention is mentioned later.

For example, in the production method described in Patent Document 1, it is conceivable that the object to be sealed is placed on the adhesive surface of an adhesive laminate such as a conventional wafer mount tape, and then the object to be sealed and its peripheral portion are placed on the adhesive surface. The adhesive surface of the 10000 is covered with a sealing material, and the sealing material is thermally cured, thereby producing a cured sealing body.

When the sealing material is thermally cured, the stress of shrinkage of the sealing material acts, but since the adhesive laminate is fixed to the support, the stress of the sealing material is suppressed.

However, it is difficult to suppress the stress which causes shrinkage of the cured sealing body obtained by separating from the support body and the adhesive laminated body. In the cured sealing body after separation, the amount of the sealing material is different between the surface side on which the object to be sealed is present and the surface side opposite thereto, and therefore, a difference in shrinkage stress is likely to occur. This difference in shrinkage stress causes warpage of the cured sealing body.

In addition, from the viewpoint of productivity, in general, the cured sealing body after heating is separated from the support body and the adhesive laminate in a state with a certain degree of heat. Therefore, after separation, the solidification of the sealing material progresses, and at the same time, shrinkage accompanying natural cooling occurs, and therefore, the cured sealing body is in a state where warpage is more likely to occur.

On the other hand, when the laminated body for warpage prevention of one embodiment of the present invention is used, a cured sealing body in which warpage is effectively suppressed can be obtained for the following reasons.

That is, when the object to be sealed is placed on the surface of the thermosetting resin layer of the laminate for preventing warpage according to one embodiment of the present invention, and the sealing material is covered with a sealing material and then thermosetting the sealing material, the thermosetting resin layer also occurs simultaneously. Heat cured. At this time, since the thermosetting resin layer is provided on the surface side of the side where the sealing object is present with a small amount of the sealing material and the shrinkage stress due to curing of the sealing material is considered to be small, the thermosetting resin layer is cured by the thermosetting resin layer. The induced shrinkage stress will come into play.

As a result, it is considered that the difference in shrinkage stress between the two surfaces of the cured seal body can be reduced, and a cured seal body in which warpage is effectively suppressed can be obtained.

In addition, the thermosetting resin layer that contributes to suppressing the warpage of the cured sealing body can be thermally cured to form a cured resin layer.

That is, by using the laminate for preventing warpage of one embodiment of the present invention and going through the above-mentioned sealing step, the cured resin layer can be simultaneously formed on one surface of the cured sealing body, so that the formation of the cured resin can be omitted. The layer process also contributes to the improvement of productivity.

Furthermore, in the laminate for warpage prevention according to one embodiment of the present invention, at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contained in the support layer (II) contains thermally expandable particles, so that the The curing of the curable resin layer (I) is completed within 2 hours and the curing minimum temperature (T ₁ ) of the cured resin layer (I′) is formed to be lower than the foaming initiation temperature (T ₂ ) of the above-mentioned thermally expandable particles. temperature. Therefore, when the heat-expandable particles are expanded by heating, the occurrence of poor peeling between the curable resin layer (I) and the support layer (II) can be prevented.

<Various Physical Properties of Laminates>

(Minimum curing temperature (T ₁ ) of curable resin layer (I))

In the laminated body for warpage prevention according to one embodiment of the present invention, at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contained in the support layer (II) contains thermally expandable particles, and is cured The curing of the resin layer (I) is completed within 2 hours and the minimum curing temperature (T ₁ ) of the cured resin layer (I′) is formed to be a temperature lower than the foaming initiation temperature (T ₂ ) of the thermally expandable particles. . Thereby, thermal expansion of the heat-expandable particles can be suppressed during the period when the curable resin layer is heated and cured. As a result, when the thermally expandable particles are thermally expanded, the adhesiveness between the curable resin layer (I) and the support layer (II) can be prevented from being excessively increased, and the occurrence of poor peeling between the two can be prevented.

Although it is not limited to this as one of the reasons why peeling failure can be suppressed, the following is presumed. During the heating and curing of the curable resin layer, when the thermally expandable particles thermally expand, irregularities are generated at the interface with the curable resin layer, and the curable resin layer is strongly adhered to the irregularities by curing. Therefore, even if the heat-expandable particle is heated and expanded after the curable resin layer is cured, the releasability with respect to the cured resin layer is considered to decrease. On the other hand, in the laminate of the present embodiment, the thermal expansion of the thermally expandable particles is suppressed while the curable resin layer is heated and cured. The thermally expandable particles thermally expand, and even if sufficient irregularities are formed in the interface with the cured resin layer, the releasability between the two can be sufficiently ensured.

The difference (T ₂ -T ₁ ) between the curing minimum temperature (T ₁ ) of the curable resin layer (I) and the foaming initiation temperature (T ₂ ) of the thermally expandable particles is preferably 20 to 100° C., and more preferably 20 to 20°C. 90°C, more preferably 20 to 80°C. By setting the temperature difference T ₂ -T ₁ in the above temperature range, a sufficient temperature difference can be set, and as a result, peeling failure can be easily suppressed, and the degree of freedom in selecting the physical properties and materials of the thermally expandable fine particles can be increased.

(Adhesion of the first surface of the curable resin layer (I))

In the laminate of one embodiment of the present invention, from the viewpoint of making the adhesiveness with the object to be sealed good, the surface of the curable resin layer (I) on which the object to be sealed is placed (first surface) is adhesive.

The adhesive force of the 1st surface of the curable resin layer (I) was affixed to a glass plate at a temperature of 70° C., at a temperature of 23° C., a peeling angle of 180°, and a peeling speed of 300 mm. 1.7N/25mm or more is preferable, 2.3N/25mm or more is more preferable, 3.0N/25mm or more is still more preferable, and 4.0N/min 25 mm or more, and preferably 20 N/25 mm or less, more preferably 15 N/25 mm or less, and still more preferably 10 N/25 mm or less.

When the adhesive force of the first surface of the curable resin layer (I) is 1.7 N/25 mm or more, when the object to be sealed is fixed to the surface of the curable resin layer (I), displacement of the object to be sealed is easily prevented. When the adhesive force of the 1st surface of the curable resin layer (I) is 20 N/25 mm or less, selection of the material of the curable resin layer (I) becomes easy.

(Shearing force of curable resin layer (I))

In the laminate of one embodiment of the present invention, it is preferable that the curable resin layer (I) has a suitable shearing force from the viewpoint of keeping the sealing object well when the sealing object is sealed. Specifically, the shear strength of the curable resin layer (I) with respect to the adherend for measurement is preferably 20 N/(3 mm×3 mm) or more, more preferably 25 N/(3 mm×3 mm), and even more preferably 30 N/ (3mm×3mm) or more, and preferably 100N/(3mm×3mm) or less, more preferably 90N/(3mm×3mm) or less, the shear strength is a silicon chip ( Mirror surface) As the above-mentioned adherend for measurement, when the mirror surface of the above-mentioned adherend for measurement is pressed at 130 gf for 1 second at a temperature of 70° C. to adhere to the above-mentioned curable resin layer, and the measurement is performed at a speed of 200 μm/s value of .

When the shear strength of the curable resin layer (I) with respect to the adherend for measurement is 20 N/(3 mm×3 mm) or more, the object to be sealed is fixed on the surface of the curable resin layer (I) and sealed with When the material covers the sealing object, it is easy to prevent the sealing object from being displaced or inclined due to the flow of the sealing material. Moreover, when the said shear strength is 100 N/(3mm*3mm) or less, selection of the material of the curable resin layer (I) becomes easy.

(Adhesion of thermosetting resin layer (X1))

In the laminate of one embodiment of the present invention, the adhesive strength of the thermosetting resin layer (I) alone at room temperature (23° C.) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm , more preferably 0.4 to 6.0 N/25mm, still more preferably 0.5 to 4.0 N/25mm.

When the laminated body 4 shown in FIG. 4 has the 1st thermosetting resin layer (X1-1) and the 2nd thermosetting resin layer (X1-2), it is preferable that they each have the above-mentioned adhesive force, especially, It is preferable to make the adhesive force of the 2nd thermosetting resin layer (X1-2) higher than the adhesive force of the 1st thermosetting resin layer (X1-1). By making the adhesive force of the second thermosetting resin layer (X1-2) higher than the adhesive force of the first thermosetting resin layer (X1-1), the object to be sealed can be more reliably fixed to the curable resin layer (I) 1st surface.

(Adhesion of the energy ray-curable resin layer (X2))

In the laminate of one embodiment of the present invention, the adhesive force of the energy ray-curable resin layer (X2) alone at room temperature (23° C.) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25mm, more preferably 0.4 to 6.0N/25mm, still more preferably 0.5 to 4.0N/25mm.

(Adhesive force of adhesive layer (V))

In the laminate of one embodiment of the present invention, the pressure-sensitive adhesive layer (V) (the first pressure-sensitive adhesive layer (V1) and the second pressure-sensitive adhesive layer) as the support layer (II) at room temperature (23° C.) The adhesive force of the layer (V2)) is preferably 0.1 to 10.0 N/25 mm, more preferably 0.2 to 8.0 N/25 mm, still more preferably 0.4 to 6.0 N/25 mm, still more preferably 0.5 to 4.0 N/25 mm. In addition, in the following description, whether it is a single pressure-sensitive adhesive layer or a plurality of pressure-sensitive adhesive layers, the pressure-sensitive adhesive layer located on the side of the curable resin layer (I) may be referred to as a first pressure-sensitive adhesive. The layer and the pressure-sensitive adhesive layer located on the opposite side of the curable resin layer are referred to as a second pressure-sensitive adhesive layer.

When the support layer (II) has the first pressure-sensitive adhesive layer (V1-1) or (V1) and has the second pressure-sensitive adhesive layer (V1-2) or (V2), the first pressure-sensitive adhesive is preferred The adhesive force of the layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2) is in the above-mentioned range, respectively, but from the improvement of the adhesion with the support, the interface can be From the viewpoint of easier separation of P at one time, it is more preferable that the adhesive force of the first pressure-sensitive adhesive layer (V1-1) or (V1) attached to the support is higher than that of the second pressure-sensitive adhesive layer (V1- 2) or (V2) adhesion.

(Measurement of the adhesive force of the first surface of the curable resin layer (I))

In this specification, the adhesive force of the 1st surface of the curable resin layer (I) can be measured by the following procedure.

First, the laminate for warpage prevention including the curable resin layer (I) and the support layer (II) was cut into a 25 mm wide×250 mm long (MD direction: 250 mm) to prepare a primary sample. Moreover, as a to-be-adhered body, the glass plate (U-Kou Shokai Co., Ltd. float glass plate 3mm (JIS R3202 product)) was prepared. A test piece was obtained by affixing a glass plate to the first surface of the curable resin layer (I) in direct contact using a lamination apparatus (manufactured by Taisei Laminator Co., Ltd., type VA-400). At this time, the conditions of a roll temperature of 70° C. and a sticking speed of 0.2 m/min were set. After the test piece thus obtained was allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity), in the same environment, according to JIS Z 0237:2000, a tensile load measuring machine (manufactured by A&D Corporation, Tensilon) was used. ) The test piece was peeled off from the glass plate under the conditions of a peeling angle of 180°, a peeling speed of 300 mm/min, and a peeling temperature of 23° C., and the adhesive force thereof was measured, and the measured value was taken as the first value of the curable resin layer (I). surface adhesion.

(Measurement of Shear Force of Curable Resin Layer (I))

In the present specification, the shear force of the curable resin layer (I) can be measured in the following procedure.

First, a silicon chip having a thickness of 350 μm having a mirror surface of 3 mm×3 mm was used as an adherend for measurement. Then, at a temperature of 70° C., the mirror surface of the adherend for measurement was pressed at 130 gf for 1 second, and was adhered to the curable resin layer (I) of each laminate obtained in each Example and Comparative Example described later. 1st surface. Next, the shear force was measured at a speed of 200 μm/s using a universal push-pull force tester (DAGE4000, manufactured by Nordson Advanced Technology).

(Measurement of Adhesive Strength of Adhesive Layer (V), Thermosetting Resin Layer (X1), and Energy Ray Curable Resin Layer (X2))

On the surface of the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy ray-curable resin layer (X2) formed on the release film, a pressure-sensitive adhesive tape (manufactured by Lintec Co., Ltd., product name "PL") is laminated. CHINE").

Next, the surface of the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy ray-curable resin layer (X2) exposed after peeling off the release film is attached to a glass plate (U-Kou Shokai Co., Ltd. float glass plate 3mm (JIS R3202 product)). At this time, the bonding temperature of the pressure-sensitive adhesive layer (V) was 23°C, and the bonding temperature of the thermosetting resin layer (X1) and the energy ray-curable resin layer (X2) was 70°C. Furthermore, after the above-mentioned glass plate with each layer attached was allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity), in the same environment, according to JIS Z 0237:2000, by the 180° peeling method, the Tensile speed 300 mm/min. The pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy ray-curable resin layer (X2) together with the pressure-sensitive adhesive tape was peeled off from the glass plate above, thereby measuring the tensile strength at 23°C. adhesion.

(Peeling force before expansion treatment (F ₀ ))

The support layer (II) and the curable resin layer (I) are preferred from the viewpoint of sufficiently fixing the object to be sealed before the curable resin layer (I) is cured and before the expansion treatment so as not to adversely affect the sealing operation. of high adhesion.

From the viewpoints described above, in the laminate of one embodiment of the present invention, the support layer (II) and the curable resin layer (I) are formed between the support layer (II) and the curable resin layer (I) before the curing of the curable resin layer (I) and before the heat expansion treatment is performed. The peel force (F ₀ ) at the time of separating the interface P is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, still more preferably 160 mN/25 mm or more, and preferably 50,000 mN/25 mm or less.

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

(Measurement of peel force (F ₀ ))

After the laminate was allowed to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity), the support layer (II) side of the laminate was attached to a glass plate (U-Kou Shokai Co., Ltd.) via an adhesive layer. Float glass plate 3mm (JIS R3202 product)). In addition, an adhesive tape (manufactured by Lintec Co., Ltd., product name "PL CHINE") was pasted on the first surface side of the laminate. Next, the edge part of the said glass plate with which the laminated body was stuck was fixed to the lower chuck|zipper of the universal tensile tester (Orientec Co., Ltd. make, product name "TENSILON UTM-4-100").

Next, the curable resin layer (I) adhered to the laminated body was adhered with the upper chuck of the universal tensile tester so that the interface P of the support layer (II) of the laminated body and the curable resin layer (I) was peeled off. ) at the end of the adhesive tape. Then, in the same environment as above, based on JIS Z 0237:2000, the curable resin layer (I) and the adhesive tape were separated from the support layer ( II) The peeling force measured at the time of peeling was taken as "peeling force (F ₀ )".

(Peeling force after expansion treatment (F ₁ ))

In the laminate of one embodiment of the present invention, the support layer (II) and the curable resin layer (I) or the cured resin layer (I) formed by curing the curable resin layer (I) can be formed by the expansion treatment. ') of the interface P with a small force to separate them at one time and easily.

Here, in the laminate according to one embodiment of the present invention, the support layer (II) and the cured resin layer (I) are formed by curing the curable resin layer (I) to form the cured resin layer (I′) by expansion treatment. The peel force (F ₁ ) at the time of separation at the interface P of the It is 100mN/25mm or less, More preferably, it is 50mN/25mm or less, Most preferably, it is 0mN/25mm.

When the peeling force (F ₁ ) is 0 mN/25 mm, even if the peeling force is to be measured, the peeling force is too small and cannot be measured.

In addition, peeling force (F1 ₎ is the value measured by the following measurement method.

(Measurement of peel force (F ₁ ))

The support layer (II) side of the laminated body was bonded to a glass plate (float glass plate 3 mm (JIS R3202 product) manufactured by U-Kou Shokai Co., Ltd.) via an adhesive layer. Next, curable resin layer (I) was hardened by heating the said glass plate and laminated body at 130 degreeC for 2 hours, and cured resin layer (I') was formed. When the curable resin layer (I) includes the energy-ray-curable resin layer (X2) as in the laminate 4 of FIG. 4, the energy-ray-curable resin layer (X1-1) can be irradiated after thermosetting The energy ray for curing the resin layer (X2) (in the case of ultraviolet rays, irradiated three times with an illuminance of 215 mW/cm ² and a light intensity of 187 mJ/cm ² ) cures the energy ray-curable resin layer (X2).

Next, the thermally expandable particles contained in the support layer (II) are expanded. Specifically, the glass plate to which the laminated body is attached is heated at 240° C. for 3 minutes to expand the thermally expandable particles in the expandable base material layer (Y1) or the expandable pressure-sensitive adhesive layer (V2) of the laminated body. Next, an adhesive tape (manufactured by Lindeco Co., Ltd., product name "PLCHINE") was attached to the first surface side of the laminate, and the measurement of the peeling force (F ₀ ) was carried out in the same manner as in the measurement of the above-mentioned peeling force (F 0 ). The peeling force measured when the interface P of the layer (II) and the cured resin layer (I') was peeled was taken as "peeling force (F ₁ )".

In addition, in the measurement of peeling force (F1), when fixing the edge part of the adhesive tape stuck to the cured resin layer ( _I ') of the laminated body with the upper clamp of the universal tensile tester , when the cured resin layer (I') was completely separated at the interface P and fixing for measurement was not possible, the measurement was terminated, and the peel force (F ₁ ) at this time was regarded as "0 mN/25 mm".

(Probe tack value of substrate (Y))

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

则判断该基材为“非粘合性的基材”。另一方面，在上述探针粘性值为

以上时，判断该基材为“粘合性的基材”。In one embodiment of the present invention, when determining whether or not it is a non-adhesive substrate, if the probe tack value measured based on JIS Z 0237:1991 with respect to the surface of the target substrate is lower than

Then, the substrate was judged to be a "non-adhesive substrate". On the other hand, in the above probe viscosity value,

In the above cases, the base material was judged to be an "adhesive base material".

优选低于

更优选低于

进一步优选低于

The support layer (II) used in one embodiment of the present invention has a probe tack value of the surface of the substrate (Y) that is generally lower than

preferably below

More preferably less than

More preferably less than

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

(Measurement of probe viscosity value)

After cutting the base material to be measured into a square with a side length of 10 mm, it was left to stand for 24 hours in an environment of 23° C. and 50% RH (relative humidity), and the obtained sample was used as a test sample. In an environment of 23°C and 50% RH (relative humidity), using a viscosity tester (manufactured by Nippon Special Instruments Co., Ltd., product name "NTS-4800"), a probe for measuring the surface of a test sample based on JIS Z0237:1991 stickiness value. Specifically, after a stainless steel probe having a diameter of 5 mm was brought into contact with the surface of the test sample at a contact load of 0.98 N/cm ² for 1 second, the probe was separated from the surface of the test sample at a speed of 10 mm/sec. The required force was used as the probe tack value of the test sample.

Next, each layer which comprises the laminated body for warpage prevention which concerns on one Embodiment of this invention is demonstrated.

<Curable resin layer (I)>

The laminated body for warpage prevention which concerns on one Embodiment of this invention has a curable resin layer (I) containing a thermosetting resin layer (X1).

The curable resin layer (I) is cured to reduce the difference in shrinkage stress between the two surfaces of the cured sealing body accompanying the curing of the sealing material, thereby contributing to suppressing warpage that may occur in the obtained cured sealing body .

The curable resin layer (I) becomes a cured resin layer (I') by curing. The cured resin layer (I') is formed on the surface of one side of the obtained cured sealing body.

As described above, the curing minimum temperature (T ₁ ) at which the curing of the curable resin layer (I) is completed within 2 hours and formed into the cured resin layer (I′) is lower than the thermal expansion contained in the support layer (II) The temperature of the foaming initiation temperature (T ₂ ) of the flexible particles. Such physical properties are mainly derived from the thermosetting resin layer (X1) contained in the curable resin layer (I).

The storage modulus E' at 23°C of the cured resin layer (I') is preferably 1.0×10 ⁷ from the viewpoint of suppressing warpage and obtaining a warpage preventing laminate capable of producing a cured sealing body having a flat surface. Pa or more, more preferably 1.0×10 ⁸ Pa or more, still more preferably 1.0×10 ⁹ Pa or more, still more preferably 5.0×10 ⁹ Pa or more, and preferably 1.0×10 ¹³ Pa or less, more preferably 1.0× 10 ¹² Pa or less, more preferably 5.0×10 ¹¹ Pa or less, still more preferably 1.0×10 ¹¹ Pa or less.

The storage modulus E' of the cured resin layer (I') can be measured in the following procedure.

First, the curable resin layer (I) is laminated to a thickness of 200 μm, and then cured until the curing is almost completed (in the measurement using a differential scanning calorimetry analyzer, the exothermic peak at 130° C. disappears time). In the case of the thermosetting resin layers (X1), (X1-1), and (X1-2), the thermosetting resin layers with a thickness of 200 μm are heated by placing them in an oven in the atmosphere and heating the resins at 130° C. for 2 hours. cured. In the case where the energy ray-curable resin layer (X2) and the thermosetting resin layer (X1-1) are included, energy rays are irradiated (in the case of ultraviolet rays, the irradiation is performed three times with an illuminance of 215 mW/cm ² and a light intensity of 187 mJ/cm ² ) On the other hand, after curing the energy ray-curable resin layer (X2), the thermosetting resin layer (X1-1) is thermally cured under the above conditions.

Next, using a dynamic viscoelasticity measuring apparatus (manufactured by TA Instruments, product name "DMAQ800"), measurement was performed under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a temperature increase rate of 3°C/min, a frequency of 11 Hz, and an amplitude of 20 μm. Storage modulus E' of the formed cured resin layer at 23°C.

The surface on the opposite side to the support layer of the curable resin layer (I), that is, the first surface has adhesiveness. In addition, the adhesive force is preferably 1.7 N/25 mm or more as described above, and the adhesive force is obtained by adhering the first surface to a glass plate at a temperature of 70° C., at a temperature of 23° C., a peeling angle of 180°, and a peeling speed. 300 mm/min The value at the time of peeling the said curable resin layer and measuring.

In addition, in this specification, in the measurement of the adhesive force of the curable resin layer (I), "sticking at a temperature of 70° C." means pressing with a pressure roller or the like whose exothermic temperature is 70° C. The press presses the laminated body to the glass plate, and affixes the laminated body to the glass plate.

The object to be sealed is placed on the above-mentioned first surface of the curable resin layer (I), but since the surface of the curable resin layer (I) has the above-mentioned adhesiveness, the adhesion to the object to be sealed is good and can be Prevents the object to be encapsulated from being skewed when the object to be encapsulated such as a semiconductor chip is disposed on the first surface, or the position of the object to be encapsulated relative to the curable resin layer (I) after disposition of the object to be encapsulated is prevented from an intended position Misalignment occurs.

In addition, the shear strength of the curable resin layer (I) with respect to the adherend for measurement is preferably 20 N/(3 mm×3 mm) or more, and the shear strength is a silicon chip (mirror surface) having a thickness of 350 μm and a size of 3 mm×3 mm. ) As the above-mentioned adherend for measurement, at a temperature of 70°C, the mirror surface of the above-mentioned adherend for measurement is pressed at 130 gf for 1 second to adhere to the above-mentioned curable resin layer, and the measurement is carried out at a speed of 200 μm/s. value.

The adhesive force of the first surface of the curable resin layer (I) and the shear force of the curable resin layer (I) with respect to the adherend for measurement can be determined by the composition of the curable resin layer (I) The types and compounding ratios of the components of the thermosetting resin composition and the energy ray-curable resin composition are adjusted so that they fall within the above-mentioned numerical range. The adhesive force and the shearing force vary depending on the components of the resin composition, the blending ratio, etc., and the shearing force also varies depending on the structure of the entire layer of the curable resin layer (I). The acrylic polymer mentioned later is used as a polymer component, an epoxy resin is used as a thermosetting component, or a coupling agent is used, and it becomes easy to make a high value. In addition, the shear force can be easily increased to a high value by, for example, increasing the content of an inorganic filler and a crosslinking agent.

The thickness of the curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, still more preferably 10 to 200 μm, still more preferably 15 to 100 μm.

(Thermosetting resin layer (X1))

The thermosetting resin layers (X1), (X1-1), and (X1-2) are preferably formed from a thermosetting resin composition containing a polymer component (A) and a thermosetting component (B). The thermosetting resin layers (X1), (X1-1), and (X1-2) may be collectively referred to as a thermosetting resin layer (X1).

The curable resin composition may further contain at least one selected from the group consisting of a colorant (C), a coupling agent (D), and an inorganic filler (E). It is preferable to contain at least an inorganic filler (E) from a viewpoint of suppressing a warpage and obtaining the laminated body for warpage prevention which can manufacture the cured sealing body which has a flat surface.

For the thermosetting resin layer (X1), it is preferable that the curing minimum temperature (T ₁ ) of the thermosetting resin layer (X1) itself to be cured within 2 hours and formed into the cured resin layer (I′) is lower than that of the support layer ( The foaming initiation temperature (T ₂ ) of the heat-expandable particles contained in II) is such that the minimum curing temperature (T ₁ ) of the curable resin layer (I) can satisfy the above relationship. The minimum curing temperature (T ₁ ) of the thermosetting resin layer (X1) is preferably lower than the foaming initiation temperature (T ₂ ) of the thermally expandable particles by 20°C or more, more preferably 25°C or more, and further preferably 30°C or more.

In order to lower the minimum curing temperature, it is sufficient to add a curing accelerator, or increase the amount of the curing accelerator and the cross-linking agent, or select a material that is more likely to be cross-linked as a monomer.

The thickness of the thermosetting resin layer (X1) may be in the same numerical range as the thickness of the curable resin layer (I).

When the thermosetting resin layer (X1) contains a plurality of layers as in the thermosetting resin layers (X1-1) and (X1-2), their thickness is such that the total thickness is the same as the thickness of the curable resin layer (I) range of values. In addition, the thickness of the thinnest layer among these layers is preferably 10% or more of the thickness of the thickest layer, more preferably 20% or more, and further preferably 30% or more.

The curing initiation temperature of the thermosetting resin layer (X1) is preferably 80 to 200°C, more preferably 90 to 160°C, further preferably 100 to 150°C.

As the thermosetting resin layer (X1), a layer whose curing initiation temperature is lower than the expansion initiation temperature of thermally expandable particles is used. The curing initiation temperature of the thermosetting resin layer (X1) is preferably lower than the expansion initiation temperature of the thermally expandable particles by 5°C or lower, more preferably 10°C or lower, and further preferably 20°C or lower.

(polymer component (A))

The polymer component (A) contained in the thermosetting resin composition means a compound having a weight average molecular weight of 20,000 or more and having at least one repeating unit.

By containing the polymer component (A) in the thermosetting resin composition, the thermosetting resin layer to be formed can have flexibility and film-forming properties, and the property retention of the laminate can be improved.

The weight average molecular weight (Mw) of the polymer component (A) is preferably 20,000 or more, more preferably 20,000 to 3,000,000, more preferably 50,000 to 2,000,000, still more preferably 100,000 to 1,500,000, and still more Preferably, it is 200,000 to 1,000,000.

The content of the component (A) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, and even more preferably 10 to 30% by mass relative to the total amount (100% by mass) of the active ingredients in the thermosetting resin composition.

Examples of the polymer component (A) include acrylic polymers, polyesters, phenoxy-based resins, polycarbonates, polyethers, polyurethanes, polysiloxanes, rubber-based polymers, and the like.

These polymer components (A) may be used alone or in combination of two or more.

It should be noted that, in this specification, the acrylic polymer having an epoxy group and the phenoxy resin having an epoxy group are thermosetting, but these resins have a weight average molecular weight of 20,000 or more and have at least one A compound with a repeating unit is considered to be included in the concept of the polymer component (A).

Among these, it is preferable that the polymer component (A) contains the acrylic polymer (A1).

The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100% by mass relative to the total amount (100% by mass) of the polymer component (A) contained in the thermosetting resin composition , 70-100 mass % is more preferable, 80-100 mass % is further more preferable, 90-100 mass % is still more preferable.

(acrylic polymer (A1))

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

From the viewpoint of imparting good adhesiveness to the surface of the thermosetting resin layer to be formed, and from the viewpoint of improving the reliability of the cured sealing body with the cured resin layer produced using the laminate for preventing warpage, the acrylic polymer The glass transition temperature (Tg) of (A1) is preferably -60 to 50°C, more preferably -50 to 30°C, still more preferably -40 to 10°C, and still more preferably -35 to 5°C.

Examples of the acrylic polymer (A1) include polymers containing alkyl (meth)acrylates as a main component, and specifically, those containing (methyl) derived from an alkyl group having 1 to 18 carbon atoms are preferred. ) An acrylic polymer of the structural unit (a1) of an alkyl acrylate (a1') (hereinafter also referred to as "monomer (a1')"), more preferably an acrylic polymer containing the structural unit (a1) and a The acrylic copolymer of the structural unit (a2) of a functional group monomer (a2') (henceforth "monomer (a2')").

The acrylic polymer (A1) may be used alone or in combination of two or more.

In addition, when the acrylic polymer (A1) is a copolymer, the form of this copolymer may be any form among a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

From the viewpoint of imparting flexibility and film-forming properties to the thermosetting resin layer to be formed, the number of carbon atoms of the alkyl group contained in the monomer (a1') is preferably 1 to 18, more preferably 1 to 12, and still more preferably 1 to 8. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

These monomers (a1') may be used alone or in combination of two or more.

The monomer (a1') preferably contains a (methyl) group having an alkyl group having 1 to 3 carbon atoms, from the viewpoint of improving the reliability of the cured sealing body with a cured resin layer produced using the laminate for preventing warpage. The alkyl acrylate, more preferably, contains methyl (meth)acrylate.

From the above-mentioned viewpoint, the structural unit (a11) derived from the (meth)acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms relative to all the structural units (100% by mass) of the acrylic polymer (A1). ) is preferably 1 to 80 mass %, more preferably 5 to 80 mass %, further preferably 10 to 80 mass %.

In addition, the monomer (a1') preferably contains an alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms, more preferably an alkyl (meth)acrylate having an alkyl group having 4 to 6 carbon atoms The ester, more preferably, contains butyl (meth)acrylate.

From the viewpoints described above, (methyl) derived from an alkyl group having 4 or more carbon atoms (preferably 4 to 6, more preferably 4) with respect to all structural units (100% by mass) of the acrylic polymer (A1). 1-70 mass % is preferable, as for content of the structural unit (a12) of alkyl) acrylate, 5-65 mass % is more preferable, 10-60 mass % is further more preferable.

The content of the structural unit (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, and further preferably 55 to 90% by mass relative to the total structural units (100% by mass) of the acrylic polymer (A1). , more preferably 60 to 90 mass %.

The monomer (a2') is preferably at least one selected from a hydroxyl group-containing monomer and an epoxy group-containing monomer.

It should be noted that the monomer (a2') may be used alone or in combination of two or more.

Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as hydroxybutyl, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol, etc.

Among these, as a hydroxyl group-containing monomer, hydroxyalkyl (meth)acrylate is preferable, and 2-hydroxyethyl (meth)acrylate is more preferable.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate Epoxy group-containing (meth)acrylates such as 3-epoxycyclo-2-hydroxypropyl (meth)acrylate; glycidyl crotonate, allyl glycidyl ether, etc.

Among these, as an epoxy group-containing monomer, an epoxy group-containing (meth)acrylate is preferable, and glycidyl (meth)acrylate is more preferable.

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

In addition, the acrylic polymer (A1) may have a structural unit derived from another monomer other than the said structural unit (a1) and (a2) in the range which does not impair the effect of this invention.

As other monomers, vinyl acetate, styrene, ethylene, α-olefin, etc. are mentioned, for example.

(Thermosetting component (B))

The thermosetting component (B) functions to thermoset the formed thermosetting resin layer to form a hard cured resin layer, and is a compound having a weight average molecular weight of less than 20,000.

The weight average molecular weight (Mw) of the thermosetting component (B) is preferably 10,000 or less, and more preferably 100 to 10,000.

As the thermosetting component (B), from the viewpoint of obtaining a laminate for preventing warpage capable of suppressing warpage and producing a cured sealing body having a flat surface, it is preferable to include an epoxy compound (B1) as a compound having an epoxy group, and The thermosetting agent (B2) more preferably contains a curing accelerator (B3) together with the epoxy compound (B1) and the thermosetting agent (B2).

Examples of the epoxy compound (B1) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolak epoxy resins, and dicyclopentadiene epoxy resins. , Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other epoxy compounds with more than 2 functions in the molecule and a weight average molecular weight of less than 20,000 Wait.

The epoxy compound (B1) may be used alone or in combination of two or more.

The epoxy compound ( The content of B1) is preferably 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, still more preferably 10 to 150 parts by mass, still more preferably 20 to 120 parts by mass.

The thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1).

As a thermosetting agent, the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is preferable.

As this functional group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an acid anhydride, etc. are mentioned. Among these, a phenolic hydroxyl group, an amino group, or an acid anhydride is preferable, and a phenolic hydroxyl group or an amino group is more preferable from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin layer having a flat surface. , more preferably an amino group.

Examples of the phenolic thermosetting agent having a phenolic hydroxyl group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, XYLOK-type phenolic resins, and aralkylphenolic resins.

As an amine thermosetting agent which has an amino group, dicyandiamide etc. are mentioned, for example.

These thermosetting agents (B2) may be used alone or in combination of two or more.

Content of thermosetting agent (B2) with respect to 100 parts by mass of epoxy compound (B1) from the viewpoint of obtaining an adhesive laminate capable of suppressing warpage and producing a cured sealing body with a cured resin layer having a flat surface Preferably it is 0.1-500 mass parts, More preferably, it is 1-200 mass parts.

The curing accelerator (B3) is a compound having a function of increasing the thermal curing rate when thermally curing the formed thermosetting resin layer.

Examples of the curing accelerator (B3) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2 -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxy Imidazoles such as methylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; .

These curing accelerators (B3) may be used alone or in combination of two or more.

From the viewpoint of obtaining a laminate for preventing warpage capable of suppressing warpage and producing a cured sealing body having a flat surface, curing accelerated with respect to 100 parts by mass of the total amount of the epoxy compound (B1) and the thermosetting agent (B2). The content of the agent (B3) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and even more preferably 0.3 to 4 parts by mass.

(Colorant (C))

The thermosetting resin composition used in one embodiment of the present invention may further contain a colorant (C).

The thermosetting resin layer formed of the thermosetting resin composition containing the colorant (C) can provide the effect of making it easy to judge the presence or absence of sticking of the cured resin layer from the appearance when the cured resin layer is obtained by thermal curing, and can also It provides effects such as shielding infrared rays and the like generated by peripheral devices to prevent malfunction of the sealing object (semiconductor chip, etc.).

As the colorant (C), organic or inorganic pigments and dyes can be used.

As the dye, any of acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes, and the like can be used.

Moreover, it does not specifically limit as a pigment, It can select and use suitably from well-known pigments.

Among these, black pigments are preferable from the viewpoint of good shielding properties against electromagnetic waves and infrared rays.

Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon. From the viewpoint of improving the reliability of the semiconductor chip, carbon black is preferred.

In addition, these coloring agents (C) may be used individually and may be used in combination of 2 or more types.

In addition, in the thermosetting resin composition used in one embodiment of the present invention, the content of the colorant (C) is preferably less than 8 with respect to the total amount (100 mass %) of the active ingredients in the thermosetting resin composition. quality%.

When the content of the colorant (C) is less than 8% by mass, the presence or absence of chip surface cracks and scraps can be obtained as a warpage prevention laminate with the naked eye.

From the above viewpoints, in the thermosetting resin composition used in one embodiment of the present invention, the content of the colorant (C) is preferably less than 5 with respect to the total amount (100% by mass) of the active ingredients in the thermosetting resin composition. The mass % is more preferably less than 2 mass %, still more preferably less than 1 mass %, still more preferably less than 0.5 mass %.

In addition, from the viewpoint that the cured resin layer obtained by thermosetting the formed thermosetting resin layer exhibits an effect of shielding infrared rays, etc., the colorant is 100% by weight relative to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. The content of (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and still more preferably 0.15% by mass or more.

(Coupling Agent (D))

The thermosetting resin composition used in one embodiment of the present invention may further contain a coupling agent (D).

The thermosetting resin layer formed from the thermosetting resin composition containing the coupling agent (D) can improve the adhesiveness with the sealing object when the sealing object is placed. In addition, the cured resin layer obtained by thermosetting the thermosetting resin layer can also improve the water resistance without impairing the heat resistance.

As the coupling agent (D), a compound which reacts with the functional group of the component (A) and the component (B) is preferable, and a silane coupling agent is specifically preferable.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, 3-(methacryloyloxypropyl)trimethoxysilane, 3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3-amino Propyltrimethoxysilane, N-6-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyl Triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethylsilane Oxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazole silane, and the like.

These coupling agents (D) may be used alone or in combination of two or more.

The molecular weight of the coupling agent (D) is preferably 100 to 15,000, more preferably 125 to 10,000, more preferably 150 to 5,000, still more preferably 1,75 to 3,000, and still more preferably 200 to 2,000.

The content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, further preferably 0.10 to 4% by mass, relative to the total amount (100% by mass) of the active ingredients in the thermosetting resin composition, More preferably, it is 0.15 to 2 mass %.

(Inorganic Filler (E))

The thermosetting resin composition used in one embodiment of the present invention preferably further contains an inorganic filler (E) from the viewpoint of obtaining a warpage preventing laminate capable of suppressing warpage and producing a cured sealing body having a flat surface.

By forming the thermosetting resin layer formed of the thermosetting resin composition containing the inorganic filler (E), when thermosetting the sealing material, the degree of thermosetting of the thermosetting resin layer can be adjusted so that both surfaces of the sealing body can be cured. The difference in shrinkage stress between them becomes smaller. As a result, it is possible to suppress warpage and manufacture a cured sealing body having a flat surface.

In addition, the thermal expansion coefficient of the cured resin layer obtained by thermosetting the formed thermosetting resin layer can be adjusted to an appropriate range, and the reliability of the object to be sealed can be improved. In addition, the moisture absorption rate of the cured resin layer can also be reduced.

Examples of the inorganic filler (E) include powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, etc., beads obtained by spheroidizing these, Non-thermally expandable particles such as single crystal fibers and glass fibers.

These inorganic fillers (E) may be used alone or in combination of two or more.

Among these, from the viewpoint of obtaining a laminate for preventing warpage that can suppress warpage and manufacture a cured sealing body having a flat surface, silica or alumina is preferred.

The average particle diameter of the inorganic filler (E) is preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm, from the viewpoint of improving the gloss value of the cured resin layer obtained by thermosetting the formed thermosetting resin layer. , is more preferably 0.3 to 30 μm, particularly preferably 0.5 to 10 μm.

The content of the component (E) with respect to the total amount (100% by mass) of the active ingredients in the thermosetting resin composition from the viewpoint of obtaining a warpage preventing laminate capable of suppressing warpage and producing a cured sealing body having a flat surface Preferably it is 25-80 mass %, More preferably, it is 30-70 mass %, More preferably, it is 40-65 mass %, More preferably, it is 45-60 mass %.

(other additives)

The thermosetting resin composition used in one embodiment of the present invention may further contain other additives other than the above-mentioned components (A) to (E) within a range that does not impair the effects of the present invention.

As other additives, a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion scavenger, a getter, a chain transfer agent, etc. are mentioned, for example.

Among them, the total content of other additives other than the components (A) to (E) is preferably 0 to 20% by mass, more preferably 0, relative to the total amount (100% by mass) of the active ingredients in the thermosetting resin composition. to 10% by mass, more preferably 0 to 5% by mass.

As shown in FIGS. 1 , 2 and 3 , when the curable resin layer (I) is constituted by a single layer of the thermosetting resin layer (X1), the single-layer thermosetting resin layer (X1) has the above-mentioned constitution. On the other hand, as shown in FIG. 4 , the curable resin layer (I) includes, for example, a first thermosetting resin layer (X1-1) located on the side of the support layer (II), and a first thermosetting resin layer (X1-1) located on the opposite side of the support layer (II) (No. In the case of having two or more thermosetting resin layers (X1) as in the case of the second thermosetting resin layer (X1-2) on the surface side), it is preferable that the above-mentioned two or more thermosetting resin layers (X1) are The minimum value (T _1a ) of the curing minimum temperature (T ₁ ) is a temperature lower than the foaming initiation temperature (T ₂ ) of the heat-expandable particles contained in the support layer (II). Even if the curing minimum temperatures (T ₁ ) of the plurality of layers contained in the thermosetting resin layer (X1) are different, since the curable resin layer showing the minimum value (T _1a ) among these has a lower generation temperature than the thermally expandable particles Since the minimum curing temperature (T ₁ ) of the bubble initiation temperature (T ₂ ), when the curable resin layer is cured, the expansion of the heat-expandable particles is suppressed, and excessive density with the curable resin layer can be prevented. combine. When the layer having T _1a among the plurality of layers constituting the thermosetting resin layer (X1) is arranged on the side closest to the support layer, this effect is remarkable, but even other layers among the above-mentioned plurality of layers show (T In the case of _1a ), the peelability between the cured resin layer (I') and the support layer (II) can be made less likely to be damaged. One of the reasons for this is presumed that since the other layer is cured in a state where the expansion of the thermally expandable particles is suppressed, when the thermally expansible particles are subsequently expanded, the increase is due to the presence of the other layer after curing. Peelability.

Moreover, for example, the adhesive force of the 1st thermosetting resin layer (X1-1) and the 2nd thermosetting resin layer (X1-2) may be mutually different. In this case, the second thermosetting resin layer (X1-2) on the first surface side is preferably the second thermosetting resin layer (X1-2) having a higher surface adhesive force than the first thermosetting resin layer (X1-1). In addition, as a method of making the adhesive force of the 2nd thermosetting resin layer higher than the adhesive force of the 1st thermosetting resin layer, for example, changing the kind of coupling agent and selecting the one that produces higher adhesive force can be mentioned. materials, methods for reducing the addition ratio of inorganic fillers, etc.

In addition, the shear force of the first thermosetting resin layer (X1-1) and the shear force of the second thermosetting resin layer (X1-2) may be made different, and the former may be increased. In this case, the shear force can be made larger than that of the second thermosetting resin layer (X1-2) by, for example, increasing the amount of the inorganic filler added to the first thermosetting resin layer (X1-1).

(Energy ray-curable resin layer)

As shown in FIG. 5 , the curable resin layer (I) may be provided with a thermosetting resin layer (X1-1) and an energy ray-curable resin layer (X2).

At this time, the curable resin layer (I) includes a first layer on the support layer side and a second layer on the first surface side, and the first layer is a thermosetting resin layer (X1-1), and the second layer is a Energy ray curable resin layer (X2). The thermosetting resin layer (X1-1) has the above-mentioned configuration.

The energy-ray-curable resin layer (X2) is preferably formed from an energy-ray-curable adhesive composition containing an energy-ray-curable adhesive resin and a photopolymerization initiator.

The energy ray-curable resin layer (X2) is easier to adjust to improve the adhesive force than the thermosetting resin layer, and thus it becomes easier to more reliably fix the object to be sealed to the first surface.

The energy ray-curable resin layer using such an energy-ray-curable adhesive composition is irradiated and cured in advance with energy rays, so that the curing of the curable resin layer is less likely to occur at the time of thermal curing of the sealing material to be described later. Curing shrinkage is beneficial to prevent warpage of the cured sealing body. In addition, when the thermosetting adhesive composition is heated at a high temperature, since it softens mainly in the initial stage of curing, there is a possibility of causing chip dislocation. On the other hand, the energy ray curable adhesive composition is Since the material does not soften during curing by energy ray irradiation, the occurrence of chip dislocation accompanying curing can be avoided.

In addition, as an energy ray, an ultraviolet-ray, an electron beam, radiation etc. are mentioned, However, an ultraviolet-ray is preferable from a viewpoint of the easiness of acquisition of a curable resin composition, and the easiness of the operation of an energy ray irradiation apparatus.

The energy-ray-curable adhesive composition may be a combination of energy-ray-curable adhesive resins in which polymerizable functional groups such as (meth)acryloyl groups and vinyl groups have been introduced into the side chains of the adhesive resins described above. It may also be a composition containing a monomer or oligomer having a polymerizable functional group.

In addition, these compositions preferably further contain a photopolymerization initiator.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl phenyl sulfide. , Tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, butanedione, 8-chloroanthraquinone, etc.

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

The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of the monomer or oligomer having a polymerizable functional group parts, more preferably 0.05 to 3 parts by mass, particularly preferably 0.1 to 3 parts by mass.

By making the shear force of the thermosetting resin layer (X1-1) larger than the shear force of the energy ray-curable resin layer (X2), the shear force of the entire curable resin layer (I) can be increased.

<Support Layer (II)>

The support layer (II) included in the laminate of one embodiment of the present invention preferably includes a substrate (Y) and an adhesive layer (V), and at least one of the substrate (Y) and the adhesive layer (V) is preferred. One contains thermally expandable particles. As described above, the support layer (II) is a layer that can be separated from the curable resin layer (I) by swelling treatment or the like, and functions as a temporary fixing layer.

A support layer used in one embodiment of the present invention when the layer containing thermally expandable particles is included in the structure of the base material (Y) and when it is included in the structure of the pressure-sensitive adhesive layer (V) (II) can be divided into the following methods.

- 1st form of a support layer (II): The support layer (II) which has a base material (Y), and this base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles.

The second form of the support layer (II): a second pressure-sensitive adhesive layer (V2) as an expandable pressure-sensitive adhesive layer containing heat-expandable particles is provided on one side of the base material (Y), and a second pressure-sensitive adhesive layer (V2) as an expandable pressure-sensitive adhesive layer containing heat-expandable particles is provided on the other side The support layer (II) of the 1st pressure-sensitive adhesive layer (V1) of the non-expandable pressure-sensitive adhesive layer.

(First form of support layer (II))

As a 1st form of a support layer (II), as shown in FIGS. 1-2, 4, and 5, the form in which a base material (Y) has an expandable base material layer (Y1) containing a thermally expandable particle is mentioned.

The pressure-sensitive adhesive layer (V) is preferably a non-expandable pressure-sensitive adhesive layer from the viewpoint of being able to separate easily at the interface P at one time with a small force.

Specifically, among the support layers (II) included in the laminates 1 a and 1 b shown in FIG. 1 , the laminate 4 shown in FIG. 4 , and the laminate 5 shown in FIG. 5 , the adhesive layer ( V1) is a non-expandable adhesive layer.

Moreover, in the support layer (II) which the laminated body 2a, 2b shown in FIG. 2 has, it is preferable that both the 1st pressure-sensitive adhesive layer (V1-1) and the 2nd pressure-sensitive adhesive layer (V1-2) are both It is a non-expandable adhesive layer.

By giving the base material (Y) the swellable base material layer (Y1) as in the first form of the support layer (II), the pressure-sensitive adhesive layer (V1) does not need to have swellability, and is not subject to the composition for imparting swellability, Composition and process limitations. Accordingly, when designing the pressure-sensitive adhesive layer (V1), it is possible to preferably design in consideration of properties such as adhesiveness, productivity, and economical performance other than swellability, so that it is possible to improve the pressure-sensitive adhesive layer (V1). V) design freedom.

The thickness of the base material (Y) before the expansion treatment of the first aspect of the support layer (II) is preferably 10 to 1,000 μm, more preferably 20 to 700 μm, still more preferably 25 to 500 μm, and still more preferably 30 to 300 μm.

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

In addition, in the present specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of adhesive layers, the above-mentioned “thickness of the adhesive layer (V)” refers to each The thickness of the pressure-sensitive adhesive layer (in FIG. 2 , the thicknesses of the first pressure-sensitive adhesive layer (V1-1) and the second pressure-sensitive adhesive layer (V1-2)).

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

In the first form of the support layer (II), the thickness ratio [(Y1)/(V)] of the intumescent base material layer (Y1) and the pressure-sensitive adhesive layer (V) before the expansion treatment is preferably 1,000 or less , more preferably 200 or less, still more preferably 60 or less, still more preferably 30 or less.

When the thickness ratio is 1,000 or less, a laminate can be obtained which can be separated at one time and easily with a small force at the interface P between the support layer (II) and the cured resin layer (I') by the expansion treatment.

In addition, this thickness ratio becomes like this. Preferably it is 0.2 or more, More preferably, it is 0.5 or more, More preferably, it is 1.0 or more, More preferably, it is 5.0 or more.

In addition, in the first form of the support layer (II), the base material (Y) may be a form composed of only the intumescent base material layer (Y1) as shown in FIG. 1( a ), or FIG. 1( b ) ) has an expandable base layer (Y1) on the side of the curable resin layer (I) and a non-expandable base layer (Y2) on the adhesive layer (V) side.

In the first form of the support layer (II), the thickness ratio [(Y1)/(Y2)] of the intumescent base material layer (Y1) and the non-expandable base material layer (Y2) before the expansion treatment is preferably 0.02-200, More preferably, it is 0.03-150, More preferably, it is 0.05-100.

In the first form of the support layer (II), the thickness of the support layer (II) is preferably 0.02 to 200 μm, more preferably 0.03 to 150 μm, further preferably 0.05 to 100 μm.

(Second form of support layer (II))

As a second form of the support layer (II), as shown in FIG. 3 , a first pressure-sensitive adhesive layer ( V1), the form in which the 2nd pressure-sensitive adhesive layer (V2) which is an expandable pressure-sensitive adhesive layer containing heat-expandable particles is arranged on the other side surface.

In addition, in the 2nd form of a support layer (II), the 2nd pressure-sensitive adhesive layer (V2) which is an expandable pressure-sensitive adhesive layer is in direct contact with the curable resin layer (I).

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

In the second form of the support layer (II), the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer before expansion treatment, and the first adhesive layer that is a non-expandable pressure-sensitive adhesive layer The thickness ratio [(V2)/(V1)] of the agent layer (V1) is preferably 0.1 to 80, more preferably 0.3 to 50, and further preferably 0.5 to 15.

In addition, in the second form of the support layer (II), the thickness ratio of the second pressure-sensitive adhesive layer (V2) as the expandable pressure-sensitive adhesive layer before the expansion treatment to the base material (Y) [(V2) /(Y)], preferably 0.05-20, more preferably 0.1-10, still more preferably 0.2-3.

In the second form of the support layer (II), the thickness of the support layer (II) is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 3 μm.

Hereinafter, the heat-expandable particles that may be contained in any layer constituting the support layer (II) will be described, and on this basis, the expandable base material layer (Y1) and the non-expandable base material constituting the base material (Y) will be described. The layer (Y2) and the pressure-sensitive adhesive layer (V) will be described in detail.

(thermally expandable particles)

As long as the expandable particles used in one embodiment of the present invention can expand themselves by heating to form irregularities on the adhesion surface of the pressure-sensitive adhesive layer (V2), the adhesion with the adherend can be improved. There are no special restrictions on the material of the relay drop.

Thermally expandable particles are excellent in versatility and handleability as compared with energy-ray-expandable particles and the like that expand upon irradiation with energy rays.

The average particle diameter before expansion at 23° C. of the thermally expandable particles used in one embodiment of the present invention 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 10 μm. 50μm.

In addition, the average particle diameter before expansion of thermally expandable particles refers to the volume median particle diameter (D ₅₀ ), and a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name “Mastersizer 3000”) is used. In the measured particle distribution of the thermally expandable particles before expansion, the cumulative volume frequency calculated from the particles with smaller particle diameters in the thermally expandable particles before expansion corresponds to 50% of the particle diameter.

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

In addition, the 90% particle diameter (D ₉₀ ) before expansion of the thermally expandable particles refers to the expansion measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name "Mastersizer 3000"). In the particle distribution of the thermally expandable particles before expansion, the cumulative volume frequency calculated from the particles with a small particle diameter among the thermally expandable particles before expansion corresponds to 90% of the particle diameter.

The thermally expandable particles used in one embodiment of the present invention do not need to expand when the sealing material is cured, and may have an expansion initiation temperature (t) higher than the curing temperature of the sealing material. Specifically, expansion is preferred. The starting temperature (t) is adjusted to be thermally expandable particles of 60 to 270°C.

In addition, the expansion start temperature (t) can be suitably selected according to the curing temperature of the sealing material used.

In addition, in this specification, the expansion start temperature (t) of a heat-expandable particle shows the value measured based on the method as described in an Example.

The heat-expandable particles are preferably a microencapsulated foaming agent containing an outer shell formed of a thermoplastic resin, and an encapsulated component that is encapsulated by the outer shell and vaporized when heated to a predetermined temperature.

Examples of the thermoplastic resin constituting the outer shell of the microencapsulated foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene Vinylidene chloride, polysulfone, etc.

Examples of the inner components enclosed in the outer shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, and isoheptane. , isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, cyclopentane Tridecane, hexylcyclohexane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, isotridecane, 4-methyldodecane, Isotetradecane, isopentadecane, isohexadecane, 2,2,4,4,6,8,8-heptamethylnonane, isoheptadecane, isooctadecane, isononadecane, 2,6,10,14-Tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, Pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc.

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

The expansion initiation temperature (t) of the heat-expandable particle can be adjusted by appropriately selecting the type of the encapsulation component, and it can be adjusted to be higher than the curing minimum temperature T ₁ of the curable resin layer (I).

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

<Expandable base material layer (Y1)>

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

In addition, from the viewpoint of improving the interlayer adhesion between the intumescent substrate layer (Y1) and other layers to be laminated, the surface of the intumescent substrate layer (Y1) may be subjected to an oxidation method, Surface treatment such as concavo-convex method, adhesion-facilitating treatment, or primer treatment.

Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, and examples of the unevenness method include sandblasting, solvent processing, etc.

In one embodiment of the present invention, the intumescent base material layer (Y1) preferably satisfies the following condition (1).

· Condition (1): The storage elastic modulus E′(t) of the expansible base material layer (Y1) is 1.0×10 ⁷ Pa or less at the expansion initiation temperature (t) of the thermally expansible particles.

In addition, in this specification, the storage elastic modulus E' of the intumescent base material layer (Y1) at a predetermined temperature shows the value measured by the method described in the Example.

The above-mentioned 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 interface P between the support layer (II) and the cured resin layer (I') with a small force, it is necessary that the support layer (II) is heated to a temperature equal to or higher than the expansion initiation temperature (t). ) on the side laminated with the curable resin layer (I) tends to form unevenness.

That is, in the expandable base material layer (Y1) satisfying the above condition (1), at the expansion start temperature (t), the thermally expandable particles expand and become sufficiently large, and it is easy to laminate the curable resin layer (I) The surface of the supporting layer (II) on one side is uneven.

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

From the above viewpoints, the storage elastic modulus E'(t) of the intumescent base material layer (Y1) specified in the condition (1) is preferably 9.0×10 ⁶ Pa or less, more preferably 8.0×10 ⁶ Pa or less, and further It is preferably 6.0×10 ⁶ Pa or less, and more preferably 4.0×10 ⁶ Pa or less.

In addition, from suppressing the flow of the thermally expandable particles after expansion, improving the shape retention of the unevenness formed on the surface of the support layer (II) on the side where the curable resin layer (I) is laminated, and at the interface P with The storage modulus E'(t) of the intumescent substrate layer (Y1) specified in the condition (1) is preferably 1.0×10 ³ Pa or more, and more It is preferably 1.0×10 ⁴ Pa or more, and more preferably 1.0×10 ⁵ Pa or more.

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

In addition, in the range which does not impair the effect of this invention, you may contain the additive for base materials in resin composition (y) as needed.

As a base material additive, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a coloring agent, etc. are mentioned, for example.

In addition, these base material additives may be used individually, respectively, and may be used in combination of 2 or more types.

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

With respect to the total mass (100 mass %) of the intumescent base material layer (Y1) or the total amount (100 mass %) of the active ingredients of the resin composition (y), the content of the heat-expandable particles is preferably 1 to 40 mass %, More preferably, it is 5-35 mass %, More preferably, it is 10-30 mass %, More preferably, it is 15-25 mass %.

The resin contained in the resin composition (y) as a material for forming the intumescent 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, as long as the adhesive resin and the polymerized The polymerizable compound undergoes a polymerization reaction, the obtained resin becomes a non-adhesive resin, and the expandable base material layer (Y1) containing the resin may be non-adhesive.

As a weight average molecular weight (Mw) of the said resin contained in the resin composition (y), 1,000-1 million are preferable, 1,000-700,000 are more preferable, and 1,000-500,000 are still more preferable.

In addition, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and may be any form 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 50 to 99% by mass, relative to the total mass (100% by mass) of the intumescent base material layer (Y1) or the total amount (100% by mass) of active ingredients in the resin composition (y). Preferably it is 60-95 mass %, More preferably, it is 65-90 mass %, More preferably, it is 70-85 mass %.

In addition, from the viewpoint of forming an intumescent base material layer (Y1) that satisfies the above-mentioned condition (1), the resin contained in the resin composition (y) preferably contains a resin selected from the group consisting of acrylic urethane-based resins and One or more of olefin resins.

Moreover, as said acrylic urethane resin, the acrylic urethane resin (U1) which polymerized a urethane prepolymer (UP) and a vinyl compound containing a (meth)acrylate is preferable.

(Acrylic urethane resin (U1))

As a urethane prepolymer (UP) which forms the main chain of an acrylic urethane resin (U1), the reaction product of a polyhydric alcohol and a polyhydric isocyanate is mentioned.

In addition, it is preferable that a urethane prepolymer (UP) is a prepolymer obtained by further carrying out the chain extension reaction using a chain extension agent.

Examples of polyols used as raw materials for urethane prepolymers (UP) include alkylene polyols, ether polyols, ester polyols, ester amide polyols, and ester-ether polyols. Alcohols, carbonate-type polyols, etc.

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

As the polyol used in one embodiment of the present invention, diols are preferred, ester diols, alkylene diols, and carbonate diols are more preferred, and ester diols and carbonates are still more preferred. type diol.

Examples of ester diols include polycondensates of one or two or more selected from the following diols and one or two or more selected from the following dicarboxylic acids and their acid anhydrides. Diols include: 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and other alkane diols, ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol and other alkylene glycols, etc.; the dicarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyl dicarboxylic acid Carboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chloro bridged acid, maleic acid, fumaric acid, itaconic acid, cyclohexane Alkane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid Formic acid, etc.

Specific examples include: polyethylene adipate diol, polybutylene adipate diol, poly-1,6-hexanediol adipate diol, poly-1,6-isophthalate diol Hexylene Glycol, Polyneopentyl Adipate Diol, Polyethylene Adipate Diol, Polyethylene Adipate Diol, Polybutylene Adipate Diol Diol 1,6-hexanediol ester diol, polyethylene glycol adipate diol, poly(polytetramethylene ether) adipate diol, poly(3-methyl adipate) pentanediol) diol, polyethylene azelaate diol, polyethylene sebacate diol, polybutylene azelaate diol, polybutylene sebacate diol Alcohol and polyneopentyl terephthalate diol, etc.

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

As carbonate-type diol, 1, 4- tetramethylene carbonate diol, 1, 5- pentamethylene carbonate diol, 1, 6- hexamethylene carbonate diol, 1,2-propylene carbonate diol, 1,3-propylene carbonate diol, 2,2-dimethylpropylene carbonate diol, 1,7-heptamethylene carbonate diol Alcohol, 1,8-octamethylene carbonate diol, 1,4-cyclohexane carbonate diol, etc.

As a polyvalent isocyanate used as a raw material of a urethane prepolymer (UP), aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned.

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

In addition, these polyvalent isocyanates may be trimethylolpropane adduct-type modified products, biuret-type modified products obtained by reacting with water, and isocyanurate-type modified products containing isocyanurate rings. Sexual body.

Among these, the polyvalent isocyanate used in one embodiment of the present invention is preferably a diisocyanate, and more preferably 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 one or more of alicyclic diisocyanates.

Examples of alicyclic diisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, etc., preferably isocyanurate Phorone diisocyanate (IPDI).

In one embodiment of the present invention, the urethane prepolymer (UP) that forms the main chain of the acrylic urethane resin (U1) is preferably a reaction product of a diol and a diisocyanate, and has both ends of the urethane prepolymer (UP). Linear urethane prepolymers with ethylenically unsaturated groups.

As a method of introducing an ethylenically unsaturated group into both ends of the linear urethane prepolymer, there may be mentioned a method of reacting a diol and a diisocyanate compound at the ends of the linear urethane prepolymer. A method of reacting NCO groups with hydroxyalkyl (meth)acrylates.

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

At least (meth)acrylate is contained as a vinyl compound which forms the side chain of acrylic urethane resin (U1).

As the (meth)acrylate, at least one selected from the group consisting of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate is preferred, and alkyl (meth)acrylate and (meth)acrylate are more preferred. base) hydroxyalkyl acrylate used in combination.

In the case of using an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate in combination, as the amount of the hydroxyalkyl (meth)acrylate relative to 100 parts by mass of the alkyl (meth)acrylate The mixing ratio 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, still more preferably 1.5 to 10 parts by mass.

As carbon number of the alkyl group which this alkyl (meth)acrylate has, 1-24 are preferable, 1-12 are more preferable, 1-8 are still more preferable, and 1-3 are still more preferable.

In addition, as the hydroxyalkyl (meth)acrylate, the same as the above-mentioned hydroxyalkyl (meth)acrylate for introducing ethylenically unsaturated groups into both ends of the linear urethane prepolymer can be mentioned. of those.

Examples of vinyl compounds other than (meth)acrylates include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; methyl vinyl ether and ethyl vinyl ether. Isovinyl ethers; vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, (methyl) Monomers containing polar groups such as acrylamide; etc.

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

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

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

In the acrylic urethane-based resin (U1) used in one embodiment of the present invention, as the structural unit (u11) derived from the urethane prepolymer (UP) and the structural unit (U11) derived from the vinyl compound The content ratio of u12) [(u11)/(u12)], in terms of mass ratio, is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, further preferably 30/70 to 60/ 40. More preferably, it is 35/65 to 55/45.

(olefin resin)

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

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

Among these, ethylene and propylene are preferable.

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

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

For example, examples of acid-modified olefin-based resins obtained by acid-modifying olefin-based resins include modified polymers obtained by graft-polymerizing unsaturated carboxylic acids or acid anhydrides thereof to the above-mentioned unmodified olefin-based resins. .

Examples of the above-mentioned unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaric acid, tetrahydrophthalic acid, aconitic acid, (methyl) ) acrylic acid, maleic anhydride, itaconic anhydride, glutaric anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc.

In addition, an unsaturated carboxylic acid or its acid anhydride may be used individually, and may be used in combination of 2 or more types.

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

As carbon number of the alkyl group which the said alkyl (meth)acrylate has, 1-20 are preferable, 1-16 are more preferable, and 1-12 are still more preferable.

As the above-mentioned alkyl (meth)acrylate, for example, the same compounds as those which can be selected as the monomer (a1') described later can be mentioned.

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

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

(Resins other than acrylic urethane resins and olefin resins)

In one embodiment of the present invention, resins other than the acrylic urethane-based resin and the olefin-based resin may be contained in the resin composition (y) within a range that does not impair the effects of the present invention.

Examples of such resins include vinyl-based resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalene. Polyester resins such as ethylene formate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane not belonging to acrylic urethane resins; polysulfone; Polyetheretherketone; polyethersulfone; polyphenylene sulfide; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; fluorine resins, etc.

Among them, from the viewpoint of forming an intumescent base material layer (Y1) that satisfies the above-mentioned condition (1), it is preferable that the content ratio of the resin other than the acrylic urethane-based resin and the olefin-based resin in the resin composition (y) is small Case.

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

(Solventless resin composition (y1))

As the resin composition (y) used in one embodiment of the present invention, an oligomer having an ethylenically unsaturated group having a weight average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer, A solvent-free resin composition (y1) which is formed from the above-mentioned thermally expandable particles and does not contain a solvent.

Although no solvent is blended in the solvent-free resin composition (y1), the energy-ray polymerizable monomer contributes to the improvement of the plasticity of the oligomer.

By irradiating an energy ray to the coating film formed from the solvent-free resin composition (y1), it becomes easy to form the expandable base material layer (Y1) which satisfies the said condition (1).

In addition, the kind, shape, and compounding quantity (content) of the heat-expandable particle mix|blended with the solventless resin composition (y1) are as mentioned above.

The weight average molecular weight (Mw) of the above-mentioned oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 20,00 to 40,000, still more preferably 3,000 to 35,000, and even more More preferably, it is 4,000-30,000.

In addition, as the oligomer, any oligomer having an ethylenically unsaturated group having a weight average molecular weight of 50,000 or less in the resin contained in the resin composition (y) may be used, and the above-mentioned urethane is preferred. Ester Prepolymer (UP).

In addition, as this oligomer, the modified olefin resin which has an ethylenically unsaturated group can also be used.

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

Examples of energy ray polymerizable monomers include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentenyloxy Alicyclic polymerizable compounds such as (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, and tricyclodecyl acrylate; phenylhydroxypropyl acrylate, benzyl acrylate, Aromatic polymerizable compounds such as phenol ethylene oxide modified acrylates; heterocyclic polymerizable compounds such as tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, etc. .

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

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

In one Embodiment of this invention, it is preferable that a photopolymerization initiator is further mix|blended with the solventless resin composition (y1).

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

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl phenyl sulfide. , tetramethylthiuram monosulfide, azobisisobutyronitrile, bibenzyl, diacetyl, 8-chloroanthraquinone, etc.

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

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

<Non-expandable base material layer (Y2)>

As a formation material of the non-expandable base material layer (Y2) which comprises a base material (Y), a paper, resin, metal etc. are mentioned, for example, According to the application of the laminated body of one Embodiment of this invention, it can select suitably.

Here, in one embodiment of the present invention, when the expansion of the thermally expandable particles contained in the expandable base layer (Y1) is suppressed, the non-expandable base layer ( From the viewpoint of forming irregularities on the surface on the side of Y2) and preferentially forming irregularities on the surface on the side of the pressure-sensitive adhesive layer (V1) of the intumescent base layer (Y1), it is preferable that the non-expandable base layer (Y2) has a Rigidity to the extent that it deforms due to expansion of thermally expandable particles. Specifically, the storage elastic modulus E′(t) of the non-expandable base material layer (Y2) at the temperature (t) at which the expansion of the thermally expandable particles starts is preferably 1.1×10 ⁷ Pa or more.

As a paper material, tissue paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, cellophane, etc. are mentioned, for example.

Examples of the resin include polyolefin resins such as polyethylene and polypropylene; vinyl-based resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.; polystyrene; acrylonitrile-butadiene-styrene copolymer; Cellulose triacetate; polycarbonate; polyurethane, acrylic modified polyurethane and other polyurethane resins; polymethylpentene; polysulfone; polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyetherimide, polyamide Polyimide resins such as imine; polyamide resins; acrylic resins; fluorine resins, etc.

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

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

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

In addition, as the formation method of the metal layer, for example, the method of vapor-depositing the above-mentioned metal by PVD methods such as vacuum evaporation, sputtering, and ion plating, or the method of pasting the above-mentioned metal using a conventional adhesive The method of metal foil, etc.

In addition, from the viewpoint of improving the interlayer adhesion between the non-expandable base material layer (Y2) and other layers to be laminated, when the non-expandable base material layer (Y2) contains a resin, The surface of the non-expandable base material layer (Y2) may be subjected to surface treatment, adhesion-facilitating treatment, or primer treatment by an oxidation method, a concavo-convex method, or the like similarly to the above-mentioned intumescent base material layer (Y1).

In addition, when the non-expandable base material layer (Y2) contains a resin, the above-mentioned base material additive which may be contained in the resin composition (y) may be further contained in addition to the resin.

The non-expandable base material layer (Y2) is a non-expandable layer that can be determined based on the above-mentioned method.

Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) which can be calculated by the above formula is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume, and further It is preferably less than 0.1% by volume, more preferably less than 0.01% by volume.

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

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

<Adhesive layer (V)>

The pressure-sensitive adhesive layer (V) included in the support layer (II) used in one embodiment of the present invention can be formed from the pressure-sensitive adhesive composition (v) containing a pressure-sensitive adhesive resin.

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

Hereinafter, each component which can be contained in an adhesive composition (v) is demonstrated.

In addition, even in the case where the support layer (II) has the first pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2), the The pressure-sensitive adhesive layer (V1-1) or (V1) and the second pressure-sensitive adhesive layer (V1-2) or (V2) may be composed of the pressure-sensitive adhesive composition (v) containing the following components form.

(adhesive resin)

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

The weight average molecular weight (Mw) of the adhesive resin used in one embodiment of the present invention is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and further Preferably, it is 30,000 to 1,000,000.

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

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

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

In one embodiment of the present invention, it is preferable that the adhesive resin contains an acrylic resin from the viewpoint of exhibiting excellent adhesive force.

In addition, when using the support layer (II) which has the 1st pressure-sensitive adhesive layer (V1-1) or (V1), and the 2nd pressure-sensitive adhesive layer (V1-2) or (V2), By containing the acrylic resin in the first pressure-sensitive adhesive layer (V1-1) or (V1) in contact with the curable resin layer (I), the first pressure-sensitive adhesive layer (V1-1) or (V1) can be Concavities and convexities are easily formed on the surface.

The content ratio of the acrylic resin in the adhesive resin is preferably 100% by mass relative to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (v) or the adhesive layer (V). 30-100 mass %, More preferably, it is 50-100 mass %, More preferably, it is 70-100 mass %, More preferably, it is 85-100 mass %.

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

(crosslinking agent)

In one Embodiment of this invention, when the adhesive composition (v) contains the adhesive resin which has a functional group, it is preferable to further contain a crosslinking agent.

This crosslinking agent is a component which reacts with the adhesive resin which has a functional group, and bridge|crosslinks adhesive resins with this functional group as a crosslinking origin.

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

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

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

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

(Tackifier)

In one embodiment of the present invention, the adhesive composition (v) may further contain a tackifier from the viewpoint of further improving the adhesive force.

In this specification, "tackifier" refers to an oligomer having a weight-average molecular weight (Mw) of less than 10,000 among components that assist in improving the adhesive force of the above-mentioned adhesive resin, and is distinguished from the above-mentioned adhesive composition of resin.

The weight average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and even more preferably 800 to 5,000.

Examples of the tackifier include rosin-based resins, terpene-based resins, styrene-based resins, pentene produced by thermal decomposition of naphtha, isoprene, piperine, and 1,3-pentanediol. C5-based petroleum resins obtained by copolymerization of C5 fractions such as alkene, C9-based petroleum resins obtained by copolymerization of C9 fractions such as indene and vinyltoluene generated by thermal decomposition of naphtha, and hydrogenated resins obtained by hydrogenation of these resins Wait.

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

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

The tackifier may be used alone or in combination of two or more having different softening points, structures, and the like.

Moreover, when using two or more types of tackifiers, it is preferable that the weighted average of the softening points of these multiple types of tackifiers falls within the above-mentioned range.

The content of the tackifier is preferably 0.01 to 65 mass % with respect to the total mass (100 mass %) of the active ingredients of the adhesive composition (v) or the total mass (100 mass %) of the adhesive layer (V) , 0.1-50 mass % is more preferable, 1-40 mass % is further more preferable, 2-30 mass % is still more preferable.

(Additives for Adhesives)

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

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

In addition, these additives for binders may be used individually, respectively, and may be used in combination of 2 or more types.

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

In addition, when using the support layer (II) of the said 3rd Embodiment which has the 2nd pressure-sensitive adhesive layer (V2) as an expandable pressure-sensitive adhesive layer, as an expandable pressure-sensitive adhesive layer That is, the forming material of the 2nd pressure-sensitive adhesive layer (V2) can be formed from the expandable pressure-sensitive adhesive composition (v22) which further contains the heat-expandable particle in the said pressure-sensitive adhesive composition (v).

The heat-expandable particles are as described above.

The content of the heat-expandable particles is preferably 1 with respect to the total mass (100 mass %) of the active ingredients of the intumescent adhesive composition (v22) or the total mass (100 mass %) of the expansible adhesive layer. It is -70 mass %, More preferably, it is 2-60 mass %, More preferably, it is 3-50 mass %, More preferably, it is 5-40 mass %.

On the other hand, when the pressure-sensitive adhesive layer (V) is a non-expandable pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition (v), which is a material for forming the non-expandable pressure-sensitive adhesive layer, preferably does not contain thermal expansion Sexual particles.

In the case of containing heat-expandable particles, the content thereof is preferably as small as possible, relative to the total amount (100% by mass) of the active ingredients in the adhesive composition (v) or the The total mass (100 mass %) is preferably less than 1 mass %, more preferably less than 0.1 mass %, further preferably less than 0.01 mass %, still more preferably less than 0.001 mass %.

In addition, in the laminated body 2a, 2b shown in FIG. 2, the 1st pressure-sensitive adhesive layer (V1-1) and the 2nd pressure-sensitive adhesive layer (V1-1) which are non-expandable pressure-sensitive adhesive layers are used. In the case of the support layer (II) of V1-2), the shear storage elastic modulus G′ at 23° C. of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer, at 23° C. ) is preferably 1.0×10 ⁸ Pa or less, more preferably 5.0×10 ⁷ Pa or less, and further preferably 1.0×10 ⁷ Pa or less.

When the shear storage elastic modulus G'(23) of the first pressure-sensitive adhesive layer (V1-1), which is a non-expandable pressure-sensitive adhesive layer, is 1.0×10 ⁸ Pa or less, for example, in the lamination shown in FIG. 2 In the case of structures like the bodies 2a and 2b, the expansion of the heat-expandable particles in the expandable base material layer (Y1) by the heat-expansion treatment makes it easy for the first pressure-sensitive adhesive layer (I') to be in contact with the cured resin layer (I'). The surface of V1-1) has irregularities.

As a result, it is possible to obtain a laminated body which can be separated at one time and easily with a small force at the interface P between the support layer (II) and the cured resin layer (I').

In addition, the shear storage elastic modulus G'(23) at 23 degreeC of the 1st pressure-sensitive adhesive layer (V1-1) which is a non-expandable pressure-sensitive adhesive layer is preferably 1.0×10 ⁴ Pa or more , more preferably 5.0×10 ⁴ Pa or more, and even more preferably 1.0×10 ⁵ Pa or more.

The light transmittance in wavelength 365nm of the support layer (II) which the laminated body which concerns on one Embodiment of this invention has becomes like this. Preferably it is 30 % or more, More preferably, it is 50 % or more, More preferably, it is 70 % or more. When the light transmittance is within the above range, when the curable resin layer (I) is irradiated with energy rays (ultraviolet rays) via the support layer (II), the curing degree of the curable resin layer (I) is further improved. The upper limit value of the light transmittance at a wavelength of 365 nm is not particularly limited, and can be, for example, 95% or less.

From the viewpoint of realizing the above-mentioned light transmittance, it is preferable that the base material (Y) and the pressure-sensitive adhesive layer (V) included in the support layer (II) do not contain a colorant.

When a colorant is contained, the content of the colorant is preferably as small as possible, relative to the total amount (100 mass %) of the active ingredients in the adhesive composition (v) or the total mass of the adhesive layer (V). (100 mass %), preferably less than 1 mass %, more preferably less than 0.1 mass %, further preferably less than 0.01 mass %, still more preferably less than 0.001 mass %, and the effective The total amount (100 mass %) of the ingredients or the total mass (100 mass %) of the base material (Y), the content of the colorant in the base material (Y) is preferably less than 1 mass %, more preferably less than 0.1 mass %, More preferably less than 0.01 mass %, still more preferably less than 0.001 mass %.

(object to be sealed)

Examples of the sealing object to be mounted on a part of the surface of the curable resin layer (I) include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic parts, sapphire substrates, displays, and panel substrates.

For example, 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 for preventing warpage of one embodiment of the present invention.

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

Moreover, it is preferable to mount a semiconductor chip so that the back surface on the opposite side to the circuit surface is covered with the surface of a thermosetting resin layer. In this case, after mounting, the circuit surface of the semiconductor chip is exposed.

For mounting the semiconductor chip, a known device such as a flip chip bonder and a die bonder can be used.

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

[Manufacturing method of the laminated body for warpage prevention]

The laminate for warpage prevention can be produced by the following method.

First, a curable resin layer (I) is formed by coating a curable resin composition on a release film and drying it.

When the curable resin layer (I) consists of two layers, each curable resin composition is formed on the release film of each layer, and the two layers are overlapped and aligned so that the two layers are in direct contact to prepare a laminate type. Curable resin layer. After coating the first curable resin composition on the release film and drying to form the first curable resin layer (X1-1), the first curable resin layer (X1-1) may be coated with the first curable resin composition. 2 The curable resin layer (X1-2) or (X2) is dried to prepare a laminated curable resin layer.

The curable resin layer (I) is adhered to the above-mentioned curable resin layer (I) by the adhesive layer (V) contained in the support layer (II), or the curable adhesive layer (II) is interposed therebetween. The resin layer (I) and the support layer (II) are bonded together to obtain a laminate for preventing warpage.

The support layer (II) can be produced by applying a pressure-sensitive adhesive composition on a release film and drying to form the pressure-sensitive adhesive layer (V), coating the resin material constituting the base material layer on the pressure-sensitive adhesive layer, and The base material layer is formed by drying or sticking the sheet-like base material to the pressure-sensitive adhesive layer. When the base material layer is composed of multiple layers, after the first base material layer is formed, the resin material constituting the second base material layer is applied on the first base material layer and dried to form the second base material layer. In the case of the support layer having the second pressure-sensitive adhesive layer on the second base material layer, the pressure-sensitive adhesive composition is applied and dried on the second base material layer to form the second pressure-sensitive adhesive layer. .

[The first manufacturing method of the cured sealing body]

The 1st Embodiment of the manufacturing method of the cured sealing body of this invention is a method of manufacturing a cured sealing body using the laminated body which concerns on one Embodiment of this invention, and this method includes following steps (i)-(iv).

Step (i): A sealing object is placed on a part of the first surface of the curable resin layer (I) included in the warpage preventing laminate.

Step (ii): The object to be sealed and at least the first surface of the curable resin layer (I) in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material.

Step (iii): thermosetting the sealing material to form a cured sealing body containing the sealing object, and simultaneously thermosetting the curable resin layer (I) to form a cured resin layer (I′), thereby curing sealing body.

Step (iv): The cured resin layer (I') and the support layer (II) are separated at the interface thereof by the treatment of expanding the heat-expandable particles to obtain a cured sealing body with a cured resin layer.

FIG. 6 is a schematic cross-sectional view showing a step of producing a cured sealing body with a cured resin layer, and more specifically, showing the production of a cured sealing body using the warpage preventing laminate 1 a shown in FIG. 1( b ). Cross-sectional schematic diagram of the process. Hereinafter, each of the above-mentioned steps will be described with reference to FIG. 6 as appropriate.

<Process (i)>

In the step (i), the object to be sealed is placed on a part of the surface of the curable resin layer (I) included in the laminate for preventing warpage of one embodiment of the present invention.

Fig. 6(a) shows a state in which the adhesive surface of the adhesive layer (V1) of the support layer (II) is attached to the support body 50 using the warpage preventing laminate 1b, and Fig. 6(b) shows the When the object to be sealed 60 is placed on a part of the surface of the curable resin layer (I).

In addition, although the example using the laminated body 1b shown in FIG.1(b) is shown in FIG. 6, when using the laminated body for warpage prevention of other embodiment of this invention, it is also possible to Similarly, the support body, the laminated body for warpage prevention, and the object to be sealed are stacked or placed in this order.

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

The support body is preferably stuck on the entire adhesive surface of the adhesive layer (V1) of the laminate.

Therefore, the support body is preferably in the shape of a plate. Moreover, as shown in FIG. 6, it is preferable that the area of the surface of the support body which adheres to the adhesive surface of the adhesive layer (V1) is equal to or larger than the area of the adhesive surface of the adhesive layer (V1).

The material constituting the support body can be appropriately selected in consideration of required properties such as mechanical strength and heat resistance, depending on the type of the object to be sealed, the type of 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 resins, ABS resins, acrylic resins, engineering plastics, special engineering plastics, and polyimide resins , resin materials such as polyamide-imide resins; composite materials such as glass epoxy resins, etc. Among these, SUS, glass, and silicon wafers are preferred.

In addition, as an engineering plastics, nylon, polycarbonate (PC), polyethylene terephthalate (PET), etc. are mentioned.

As special engineering plastics, polyphenylene sulfide (PPS), polyethersulfone (PES), polyetheretherketone (PEEK), etc. are mentioned.

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

On the other hand, as a sealing object to be mounted on a part of the surface of the curable resin layer (I), for example, semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic parts, sapphire substrates, displays, and panels can be mentioned. substrate, etc. In the following description, a case where a semiconductor chip is used as the sealing object 60 will be described as an example.

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 of one embodiment of the present invention.

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

Moreover, it is preferable to mount a semiconductor chip so that the back surface of the opposite side from a circuit surface may be covered with the surface of the curable resin layer (I). In this case, after mounting, the circuit surface of the semiconductor chip is exposed.

For mounting the semiconductor chip, a known device such as a flip chip bonder and a die bonder can be used.

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

The surface of the curable resin layer (I) of the present embodiment (in the example of FIG. 6 , the surface on the opposite side to the support layer (II) of the non-expandable thermosetting resin layer (X1)) is curable However, by making the adhesive force as described above, when the semiconductor chip 60 as the sealing object is bonded to the above-mentioned surface of the curable resin layer (I), the semiconductor chip 60 can be securely fixed and displacement can be easily prevented.

Here, the laminate of one embodiment of the present invention is preferably applied to a semiconductor chip, such as FOWLP, FOPLP, etc., by covering a region larger than the chip size with a sealing material so as to not only form a rewiring layer, a rewiring layer on the circuit surface of the semiconductor chip, The encapsulation of the redistribution layer is also formed in the surface area of the encapsulant.

Therefore, the semiconductor chip is placed on a part of the surface of the curable resin layer (I). Preferably, a plurality of semiconductor chips are placed on the surface in a state of being arranged with a certain interval therebetween, and more preferably a plurality of semiconductor chips are placed at a certain interval. And a matrix-like state arranged in a plurality of rows and columns is placed on the surface.

The space|interval of a semiconductor chip can be suitably determined according to the form etc. of the target package.

<Process (ii)>

In step (ii), the object to be sealed placed on the curable resin layer (I) and at least the first part of the curable resin layer (I) in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material. surface (hereinafter also referred to as "coating treatment").

In the coating process, first, the object to be sealed and at least the peripheral portion of the object to be sealed on the surface of the curable resin layer (I) are coated with a sealing material. Specifically, as shown in FIG. 6( c ), the molding die 70 is arranged such that the laminated body 1 b is placed in the mold of the molding die 70 , and the laminated body 1 b is adhered to the support body 50 as a sealing object The semiconductor chip 60 is placed on the curable resin layer (I). Next, the sealing material is injected into the molding space 72 formed between the molding die 70 , the laminated body 1 b and the sealing object 60 through the injection hole 71 .

The sealing material covers the entire exposed surface of the semiconductor chip 60 , which is an object to be sealed, and also fills the gaps between the plurality of semiconductor chips.

After the injection of the sealing resin and resin molding are completed, the molding die 70 is removed, and as shown in FIG.

It should be noted that, when the sealing material 80 is injected into the molding space 72 by a resin molding method of a type represented by transfer molding, in which a resin material is injected into a molding die, along the curable resin (I) The flow of the sealing material 80 occurs in the direction of the surface of the (see arrows in FIG. 6( c )). In the production method of the present embodiment, the object to be sealed 60 is fixed by the curable resin layer (I), and the shear strength of the curable resin layer (I) with respect to the adherend for measurement is as described above, It is easy to prevent displacement or skew of the sealing object 60 .

The sealing material has a function of protecting the sealing object and its accompanying components from the external environment.

The sealing material 80 used in the manufacturing method of one embodiment of the present invention is a thermosetting sealing material containing a thermosetting resin.

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

As the coating method, in addition to the transfer molding method, it can be appropriately selected from methods used in the conventional sealing process according to the type of the sealing material. For example, a roll lamination method, a vacuum pressing method, and a vacuum lamination method can be used. , spin coating, die coating, compression molding, etc.

<Process (iii)>

In the step (iii), the encapsulating material subjected to the coating treatment is thermally cured to form a cured sealing body including the object to be encapsulated. In addition, the curable resin layer (I) is also cured to form the cured resin layer (I').

Specifically, as shown in FIG. 6( e ), by curing the sealing material 80 , a cured sealing body 85 in which the semiconductor chip 60 as the sealing object is covered with the cured sealing material 81 is obtained. Thereby, the semiconductor chip 60 can be protected with a hard material while maintaining the layout of the semiconductor chip 60 . At this time, since the thermosetting resin layer (X1) is used as the curable resin layer (I) in the production method of the present embodiment, the curing start temperature of the thermosetting sealing material 80 is set to start the curing of the thermosetting sealing material 80 in advance. If the temperature is the same, or if the curing initiation temperature of the two is different, the curing of the sealing material and the curing (curing) of the thermosetting resin layer can be achieved by heating to the higher curing initiation temperature or higher. The formation of the subsequent thermosetting resin layer (X1') is performed simultaneously. Therefore, in these cases, the number of heating steps for curing can be reduced, and the manufacturing process can be simplified.

In addition, in the manufacturing method of the present embodiment, by providing the curable resin layer (I), the difference in shrinkage stress between the two surfaces of the obtained cured sealing body 85 can be reduced, and the generation of the cured sealing body 85 can be effectively suppressed. warping. In particular, by thermally curing the thermosetting resin layer ( X1 ) at the same time as the thermal curing of the sealing material, the difference in shrinkage stress between the two surfaces of the curing sealing body 85 can be reduced during the curing process, thereby Warpage can be suppressed more effectively.

In addition, as mentioned above, the heating temperature for hardening in a process (iii) is lower than the heating temperature for expansion in a process (iv).

<Process (iv)>

In the step (iv), the cured resin layer (I′) and the support layer (II) are separated at the interface thereof by performing a process of expanding the thermally expandable particles contained in the expandable base material layer (Y1) to obtain a Cured sealing body with cured resin layer.

Fig. 6(f) shows that the expandable base material layer (Y1) becomes an expanded base material layer (Y1') by the process of expanding the heat-expandable particles, and after the cured resin layer (I') and the expanded base material layer (Y1') The interface of the supporting layer (II') is separated.

As shown in FIG. 6( f ), by separating at the interface, a cured sealing body 200 with a cured resin layer including a cured sealing body 85 in which the sealing object 60 is sealed and a cured resin layer (I′) can be obtained .

It should be noted that the presence of the cured resin layer (I') has a function of effectively suppressing warpage of the cured sealing body, and contributes to the improvement of the reliability of the sealing object.

The "treatment to expand" in the step (iv) is a treatment to expand the thermally expandable particles by heating at or above the expansion start temperature (t), and by this treatment, the cured resin layer (I') side is The surface of the supporting layer (II) is uneven. As a result, the separation at the interface P can be easily and once achieved with a small force.

As the "temperature at or above the expansion start temperature (t)" that expands the thermally expandable particles, it is preferably not less than the "expansion start temperature (t)+10°C" or more and the "expansion start temperature (t)+60°C" or less , more preferably "expansion initiation temperature (t)+15°C" or more and "expansion initiation temperature (t)+40°C" or less.

It should be noted that the heating method for expanding the heat-expandable particles is not particularly limited, and for example, a heating method using a hot plate, an oven, a calcining furnace, an infrared lamp, a hot air blower, etc., can be exemplified. II) From the viewpoint of separation from the interface P of the cured resin layer (I'), a method in which a heat source during heating can be provided on the side of the support body 50 is preferable.

The cured sealing body 200 with the cured resin layer thus obtained may be further subjected to necessary processing. The cured resin layer as the warpage correction layer is removed by grinding or the like when the semiconductor device is finally manufactured, and does not remain in the semiconductor device as the final product.

[Second Manufacturing Method of Cured Sealing Body]

A second embodiment of the method for producing a cured sealing body of the present invention is a method for producing a cured sealing body using the laminate of one embodiment of the present invention, and the method includes the following steps (i') to (iv).

Step (i'): Place sealing on a part of the first surface of the curable resin layer included in the warpage preventing laminate, that is, a part of the surface of the energy ray-curable resin layer (X2) on the opposite side to the first layer object.

Step (ii')-1: The energy ray-curable resin layer (X2) is cured by irradiating energy rays.

Step (ii')-2: The object to be sealed and at least the first surface of the curable resin layer in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material.

Step (iii'): thermally curing the sealing material to form a cured sealing body including the above-mentioned sealing object, and simultaneously thermally curing the curable resin layer (I) to form the cured resin layer (I') and curing sealing body.

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

Hereinafter, each process will be described in detail, but in order to avoid redundancy, the descriptions in the first embodiment of the manufacturing method are directly applied to the same steps and operations as those of the first embodiment of the manufacturing method described above, and specific descriptions will be omitted.

<Process (i')>

In the step (i'), an object to be sealed is placed on a part of the surface of the curable resin layer (I) included in the laminate for preventing warpage of one embodiment of the present invention.

Fig. 7(a) shows the thermosetting resin layer (X1-1) on the side of the support layer (II) and the energy ray-curable resin layer (X1-1) on the opposite side from the support layer (II) using the curable resin layer (I). X2) The laminated body 5 (see FIG. 5 ) for preventing warpage constituted by the state where the adhesive surface of the adhesive layer (V1) of the support layer (II) is attached to the support body 50 is shown in FIG. 7(b) . A state in which the object to be sealed 60 is placed on a part of the surface of the curable resin layer (I).

The surface of the curable resin layer (I) of the present embodiment (in the example of FIG. 7 , the surface on the opposite side to the support layer (II) of the energy ray-curable resin layer (X2)) has curability, and by making The adhesive force is 1.7 N/25 mm or more in terms of the value measured below, and when the object to be sealed 60 is bonded to the above-mentioned surface of the curable resin layer (I), the object to be sealed 60 can be securely fixed, Displacement including oblique dislocation is easily prevented. The measurement is performed by attaching the above-mentioned first surface to a glass plate at a temperature of 70°C, and peeling the curable resin layer at a temperature of 23°C, a peeling angle of 180°, and a peeling speed of 300 mm/min. (I) Measurement by peeling.

<Process (ii')-1>

Step (ii')-1 is a step of irradiating the energy ray-curable resin layer (X2) with energy rays to form a cured resin layer (I ^* ) in which the energy ray-curable resin layer (X2) is cured.

Fig. 7(c) shows that in this step, the energy ray-curable resin layer (X2') after curing is formed by curing the energy-ray-curable resin layer (X2), thereby forming a partially cured (ie, , the state of the cured resin layer (I ^* ) in which the layer on the first surface side is cured).

The types and irradiation conditions of the energy rays are not particularly limited as long as the types and conditions can cure the energy ray-curable resin layer (X2) to such an extent that the functions thereof can be fully exhibited, and are appropriately selected from known methods according to the desired process. That's it.

As the material constituting the energy ray-curable resin layer (X2), when an ultraviolet-curable resin composition is used, a wide range of materials can be selected, and as an energy ray source for curing the composition, it is easy to obtain and handle Also excellent for UV irradiation devices.

The illuminance of the energy ray during curing of the energy ray-curable resin layer (X2) is preferably 4 to 280 mW/cm ² , and the light intensity of the energy ray during the curing is preferably 3 to 1,000 mJ/cm ² .

By irradiating the energy ray in the step (ii')-1 before the step (iii') including thermal curing, cracking of the energy ray-curable resin due to heating can be avoided, and the curing reaction can be prevented. The curing reaction proceeds more efficiently. In addition, low molecular weight components (photopolymerization initiators, etc.) contained in the energy ray-curable resin are volatilized by heating, and contamination of the object to be sealed can also be prevented. Furthermore, by curing the energy ray-curable resin layer with energy rays in advance before thermal curing, curing shrinkage of the energy ray-curable resin (X2) due to heating for thermal curing can be prevented, thereby preventing the sealing resin from forming a Adhesion between energy ray-curable resins (X2) decreases.

<Process (ii')-2>

After the energy ray-curable resin layer (X2') after curing is formed by arranging the sealing object 60 and irradiating the energy ray, in the step (ii')-2, it is the same as that described in FIG. 6(d) , and the sealing material 80 is injected using a molding die not shown. At this time, the flow of the sealing material in the surface direction occurs, but the sealing object 60 is fixed by the energy ray-curable resin layer (X2') after curing, and the curable resin layer (I) is relatively The shear strength of the adherend is 20N/(3mm×3mm) or more in the following measurement, which is easy to prevent displacement or distortion of the sealing object 60 with a mirror surface of 3mm×3mm. A silicon chip with a thickness of 350 μm was used as the above-mentioned adherend for measurement, and the mirror surface of the adherend for measurement was pressed and adhered to the curable resin layer (I) for 1 second at a temperature of 70° C. and 130 gf at a speed of 200 μm. /s measurements performed.

After the injection of the sealing resin is completed, as shown in FIG.

<Process (iii')>

In the step (iii'), the encapsulating material subjected to the coating treatment is thermally cured to form a cured encapsulating body including the object to be encapsulated. Further, the thermosetting resin layer (X1-1) is also cured to form a cured resin layer (X1-1'), thereby forming a cured resin layer (I') in which both the first layer and the second layer are cured.

By curing the sealing material 80 , as shown in FIG. 7( e ), a cured sealing body 85 in which the sealing object 60 is covered with the cured sealing material 81 is obtained. At this time, in this production example, since the thermosetting resin layer (X1-1) was used as the curable resin layer (I), the curing initiation temperature was set to approximately the same level as that of the thermosetting sealing material 80 in advance, Alternatively, when the curing initiation temperature is different, the curing of the sealing material and the curing of the thermosetting resin layer can be simultaneously performed by heating to the higher curing initiation temperature or higher.

<Process (iv)>

In the step (iv), the cured resin layer (I′) and the support layer (II) are separated at the interface thereof by performing a treatment of expanding the expandable particles contained in the expandable base material layer (Y1), thereby obtaining Cured sealing body with cured resin layer.

Fig. 7(f) shows that the expandable base material layer (Y1) becomes the expanded base material layer (Y1') by the process of expanding the expandable particles, after the cured resin layer (I') and the expanded support layer ( The interface of II') is separated.

As shown in FIG. 7( f ), by separating at the interface, a cured sealing body 201 with a cured resin layer including a cured sealing body 85 in which the sealing object 60 is sealed and a cured resin layer (I′) can be obtained .

After the cured sealing body 85 is produced in the above procedure, necessary processing is performed on the cured sealing body 201 with the cured resin layer.

Example

Next, specific examples of the present invention will be described, but the present invention is not limited to these examples at all.

In addition, in the following description, curable resin layer (I) represents both "energy ray-curable resin layer (X2)" and "thermosetting resin layers (X1-1), (X1-2)" .

In addition, the physical property values in the following production examples and examples are values measured by the following methods.

<Weight Average Molecular Weight (Mw)>

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

(measurement conditions)

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

·Column temperature: 40℃

Developing solvent: tetrahydrofuran

·Flow rate: 1.0mL/min

<Measurement of Thickness of Each Layer>

The measurement was performed using a constant pressure thickness gauge (model: "PG-02J", standard: based on JIS K6783, Z1702, Z1709) manufactured by TECLOCK.

<Minimum curing temperature of curable resin layer>

Using the same composition, a plurality of samples for measurement were prepared in advance, and using a differential scanning calorimeter (manufactured by TA Instruments, Q2000), the peaks attributed to the curing reaction were measured from 60°C at a set temperature of 20°C intervals. time to disappear. At this time, the temperature was raised at a temperature increase rate of 10° C./min from the normal temperature to the set temperature. In the above measurement, the temperature at which the curing reaction peak disappears in 2 hours was taken as the curing minimum temperature.

<Releasability after curing of curable resin layer>

Prepare two samples in which a curable resin layer is attached to a glass plate (float glass plate 3 mm (JISR3202 product) manufactured by U-Kou Shokai Co., Ltd.) to which a support layer is attached, and one is heated at 130° C. for 2 hours, and the other is heated at 130° C. for 2 hours. One was heated at 160°C for 1 hour. The heated samples for measurement were heated by a hot plate at the maximum expansion temperature of the support layer of each sample, which will be described later +30° C. for 3 minutes. After naturally cooling to normal temperature, the peelability between the support layer and the cured resin layer was evaluated. When the curable resin layer did not self-peel (peel without external force), the end of the curable resin layer was sandwiched with tweezers, and peeled at the interface between the support layer and the curable resin layer, and evaluated.

○ = Self-peeling occurred on the entire surface, and no abnormality was found in the appearance of the peeling surface of the cured resin layer.

Δ = Peeling with tweezers was required, and peeling was not achieved in part of the interface P, and there was no abnormality in the appearance of the peeling surface of the cured resin layer.

×=Cannot be peeled off with tweezers, or a portion that cannot be peeled off occurred on the entire surface of the curable resin layer.

<Measurement of expansion start temperature (t) and maximum expansion temperature of thermally expandable particles>

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

0.5 mg of heat-expandable particles to be measured were placed in an aluminum cup having a diameter of 6.0 mm (inner diameter 5.65 mm) and a depth of 4.8 mm, and an aluminum cap (diameter 5.6 mm, thickness 0.1 mm) was placed on the cup to prepare a sample.

Using a dynamic viscoelasticity measuring apparatus, the height of the sample was measured in a state where a force of 0.01 N was applied to the sample from the upper part of the aluminum cover with an indenter. Then, in the state where a force of 0.01 N was applied by the indenter, the temperature was increased from 20°C to 300°C at a heating rate of 10°C/min, the displacement of the indenter in the vertical direction was measured, and the displacement in the positive direction was started. The temperature is taken as the expansion onset temperature (t).

In addition, the maximum expansion temperature refers to the temperature at which the above-mentioned displacement amount reaches the maximum.

<Measurement of the expansion coefficient of the support layer at the curing temperature of the curable resin layer>

The displacement amount obtained when the above-mentioned maximum expansion temperature was measured was taken as the thickness (Dm) of the support layer at the maximum expansion temperature. In addition, for each support layer, the thickness (Da) of the support layer when heated under Curable Resin Layer Curing Condition 1 (heating at 130° C. for 2 hours), and Curable Resin Layer Curing Condition 2 ( The thickness (Db) of the support layer at the time of heating at 160 degreeC for 1 hour). Then, the values of (Da/Dm)×100 and (Db/Dm)×100 were obtained as the expansion coefficients of the support layer at the curing temperature of the curable resin layer.

<Measurement of Adhesion of Thermosetting Resin Layer>

An adhesive tape (manufactured by Lintec Co., Ltd., product name "PL CHINE") was laminated on the surface of the thermosetting resin layer formed on the release film.

Then, the peeling film was removed, and the surface of the exposed thermosetting resin layer was stuck to the smooth surface of the glass plate (U-Kou Shokai Co., Ltd. float glass plate 3 mm (JIS R3202 product)) as an adherend. The bonding temperature of the thermosetting resin layer (X1) was set to 70°C. Next, after leaving the said glass plate with each layer attached for 24 hours in an environment of 23° C. and 50% RH (relative humidity), in the same environment, based on JIS Z0237:2000, by the 180° peeling method, the The adhesive force at 23°C was measured at an elongation speed of 300 mm/min.

In addition, the release material used in the following manufacturing example is as follows.

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

Light release film: Lintec Co., Ltd., product name "SP-PET381031", material provided with a release agent layer formed of a silicone-based release agent on one side of the PET film, thickness: 38 μm

<Evaluation of warpage>

The thermosetting resin layers of the warpage preventing laminates of Examples 1 and 2 were respectively attached to a 12-inch silicon wafer with a thickness of 100 μm, and the epoxy resin composition was applied to the side opposite to the side to which the thermosetting resin layer was attached to a thickness of 30 μm. . Then, the layer of the epoxy resin composition and the thermosetting resin layer of each laminate are heated and cured. After the completion of curing, the silicon wafer with the cured resin layer was placed on a water table, and then visually observed, and the presence or absence of warpage was evaluated based on the following criteria.

A: The warpage amount is 3 mm or less.

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

C: The warpage amount is 15 mm or more.

As the epoxy resin composition, a mixture of "EpoFix Resin" manufactured by Struers and a curing agent "EpoFix Hardner" manufactured by Struers was used. It should be noted that, in this evaluation, in order to simplify the test procedure, a large-diameter silicon wafer was used as the adherend, but on the other hand, by providing an epoxy resin layer on the back side of the adherend, it is easy to form The conditions under which warpage occurs, thereby making the evaluation of warpage suitable.

Manufacturing Example 1

(1) Preparation of curable resin composition

The following types and compounding amounts (all of which are "active ingredient ratios") of the components were blended, further diluted with methyl ethyl ketone, and stirred until uniform to prepare a thermosetting resin composition with a solid content concentration (active ingredient concentration) of 61% by mass solution of the substance.

Acrylic polymer: compounding amount = 21 parts by mass

Acrylic polymer obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 80 10,000, glass transition temperature: -28°C), equivalent to the above-mentioned component (A1).

Epoxy compound (1): compounding amount = 10 parts by mass

Liquid bisphenol A epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name "BPA328", epoxy equivalent = 220 to 240 g/eq) corresponds to the above-mentioned component (B1).

Epoxy compound (2): compounding amount = 2.0 parts by mass

A solid bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "Epicoat 1055", epoxy equivalent = 800 to 900 g/eq) corresponds to the above-mentioned component (B1).

Epoxy compound (3): compounding amount = 5.6 parts by mass

Dicyclopentadiene-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "XD-1000L", epoxy equivalent = 274 to 286 g/eq) corresponds to the above-mentioned component (B1).

Thermosetting agent: compounding amount = 0.5 parts by mass

Dicyandiamide (manufactured by ADEKA Corporation, product name "ADEKA HARDNER EH-3636AS", activated hydrogen amount=21 g/eq) corresponds to the above-mentioned component (B2).

Curing accelerator: compounding amount = 0.5 parts by mass

2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "Curazole2PHZ") corresponds to the above-mentioned component (B3).

Silane coupling agent: compounding amount = 0.4 parts by mass

The epoxy group-containing oligomer type silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2") corresponds to the above-mentioned component (D).

Inorganic filler (1): compounding amount = 6 parts by mass

The spherical silica filler (manufactured by Admatechs, product name "SC2050MA", average particle diameter=0.5 μm) corresponds to the above-mentioned component (E).

Inorganic filler (2): compounding amount = 54 parts by mass

The spherical silica filler (manufactured by Ronson Co., Ltd., product name "SV-10", average particle diameter=8 μm) corresponds to the above-mentioned component (E).

(2) Formation of thermosetting resin layer

The solution of the thermosetting resin composition prepared in the above (1) 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° C. for 2 minutes to form a thermosetting resin layer with a thickness of 25 μm , which was used as the curable resin layer 1 .

In addition, the adhesive force of the thermosetting resin layer 1 formed was 0.5 N/25mm.

Manufacturing Example 2

(1) Fabrication of the support layer

A heat-peelable laminate (manufactured by Nitto Denko Co., Ltd., product name "Riva Alpha (NITTO 3195)") having a structure in which a heat-peelable adhesive layer was provided on a polyester film substrate was used as the support layer as it was . This layer was used as the support layer 1 . In addition, when producing the laminated body for warpage prevention mentioned later, the release liner provided on the surface of a thermal peeling adhesive layer was peeled and used. The support layer 1 has a pressure-sensitive adhesive layer including a base material and thermally expandable particles, and is heated to 170° C. or higher, which is an expansion start temperature, to expand the thermally expandable particles, thereby generating fine irregularities on the surface of the pressure-sensitive adhesive layer. shape.

Manufacturing Example 3

(1) Synthesis of urethane prepolymer

In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate was added with respect to 100 parts by mass (solid content ratio) of a carbonate-type diol having a weight average molecular weight of 1,000, and the hydroxyl groups of the carbonate-type diol were mixed with isophor. The ketone diisocyanate had an isocyanate group equivalent ratio of 1/1, then 160 parts by mass of toluene was added, and the reaction was carried out at 80° C. for 6 hours or more with stirring in a nitrogen atmosphere until the isocyanate group concentration reached the theoretical amount.

Next, a solution obtained by diluting 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added, and the reaction was further carried out at 80° C. for 6 hours until both ends. A urethane prepolymer with a weight average molecular weight of 29,000 was obtained until the isocyanate group disappeared.

(2) Synthesis of acrylic urethane resin

Into a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solid content ratio) of the urethane prepolymer obtained in Production Example 1, 117 parts by mass (solid content ratio) of methyl methacrylate (MMA), and methyl methacrylate (MMA) were added. 5.1 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) (solid content ratio), 1.1 parts by mass of 1-thioglycerol (solid content ratio), and 50 parts by mass of toluene, and the temperature was raised to 105°C while stirring.

Then, 2.2 parts by mass of a radical initiator (manufactured by Nippon Seika Co., Ltd., product name "ABN-E") diluted with 210 parts by mass of toluene was added dropwise to the reaction vessel over 4 hours while maintaining at 105° C. (solid content ratio).

After completion of the dropwise addition, the reaction was carried out at 105° C. for 6 hours to obtain a solution of an acrylic urethane resin having a weight average molecular weight of 105,000.

(3) Preparation of adhesive composition (1)

5.0 parts by mass (solid content ratio) of the following isocyanate-based crosslinking agent (i) was mixed with 100 parts by mass of the solid content of the following acrylic copolymer (i) as an adhesive resin, diluted with toluene, and stirred until uniform , an adhesive composition (1) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared.

Acrylic copolymer (i): the weight of the structural unit derived from the raw material monomer composed of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio) Acrylic copolymer with an average molecular weight of 600,000.

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

(4) Preparation of adhesive composition (2)

5.0 parts by mass (solid content ratio) of the following isocyanate-based crosslinking agent (i) was mixed with 100 parts by mass of the solid content of the following acrylic copolymer (i) as an adhesive resin, diluted with toluene, and stirred until uniform , an adhesive composition (2) having a solid content concentration (active ingredient concentration) of 25% by mass was prepared.

Acrylic copolymer (i): the weight of the structural unit derived from the raw material monomer composed of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio) Acrylic copolymer with an average molecular weight of 600,000.

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

(5) Formation of adhesive layer (1)

The adhesive composition (1) prepared in Production Example 3 (1) was applied to the surface of the release agent layer of the above-mentioned light release film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a coating film. Adhesive layer (1) with a thickness of 5 μm.

(6) Formation of the adhesive layer (2)

The adhesive composition (2) prepared in Production Example 3 (2) was applied to the surface of the release agent layer of the above-mentioned heavy release film to form a coating film, and the coating film was dried at 100° C. for 60 seconds to form a coating film. Adhesive layer (2) with a thickness of 10 μm.

(7) Production of support layer

The pressure-sensitive adhesive layer (2) was attached to one side of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "COSMOSHINE A4100") having a thickness of 50 μm as a base material.

Next, on the other side of the PET film, a polyester-based adhesive (glass transition temperature: -50° C., weight average molecular weight: 21,000, OH value: 4 mgKOH/g) was added to 100 parts by mass to add HDI nurate for crosslinking. The composition containing 4 parts by mass of the agent was dried at 100° C. for 1 minute to form an anchor layer with a thickness of 40 μm.

To 100 parts by mass of solid content of the acrylic urethane-based resin obtained in Production Example 3 (2), an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, product name "Coronate L", solid content concentration: 75% by mass was blended ) 6.3 parts by mass (solid content ratio), 1.4 mass parts (solid content ratio) of dioctylbis(2-ethylhexanoate) tin as a catalyst, and the above-mentioned thermally expandable particles (manufactured by Kureha Co., Ltd., product name "S2640") ", expansion start temperature (t) = 208 ℃, average particle diameter (D ₅₀ ) = 24 μm, 90% particle diameter (D ₉₀ ) = 49 μm), diluted with toluene, stirred until uniform, and prepared solid content concentration (effective Ingredient concentration) 30 mass % resin composition. The content of the heat-expandable particles was 20% by mass with respect to the total amount (100% by mass) of the active ingredients in the obtained resin composition.

The resin composition containing this heat-expandable particle was apply|coated on the said anchor layer, and a coating film was formed, and this coating film was heated at 100 degreeC for 2 minutes, and it dried, and the heat-expandable layer with a thickness of 35 micrometers was formed.

The above-mentioned pressure-sensitive adhesive layer (1) is attached to the thermally expandable layer. In this way, the support layer in which the release film was laminated on the front and back surfaces was produced, and this was used as the support layer 2 .

The support layer 2 has an adhesive layer and a base material containing heat-expandable particles, and when heated to 208° C. or higher, the heat-expandable particles are expanded to generate fine concavo-convex shapes on the surface of the support layer.

Manufacturing Example 4

The heat-expandable particles were changed to heat-expandable microcapsules manufactured by Japan Fillite Co., Ltd. (product name "Expancel 031-40DU", expansion initiation temperature (t)=80°C), and drying after coating the resin composition to form a coating film A support layer was produced in the same manner as in Production Example 3, except that the conditions were changed to an atmospheric temperature of 100° C. for 1 minute, and this was used as the support layer 3 .

The support layer 3 has an adhesive layer and a base material containing heat-expandable particles, and when heated to 80° C. or higher, the heat-expandable particles are expanded to generate fine irregularities on the surface of the support layer.

Manufacturing Example 5

The heat-expandable particles were changed to Japan Fillite Co., Ltd. heat-expandable microcapsules (product name "Expancel 053-40DU", expansion initiation temperature (t)=100°C), and the drying conditions after coating the resin composition to form a coating film were changed A support layer was produced in the same manner as in Production Example 3 except that the atmosphere temperature was 100° C. for 1 minute, and this was used as the support layer 4 .

The support layer 4 has an adhesive layer and a base material containing heat-expandable particles, and when heated to 100° C. or higher, the heat-expandable particles are expanded to generate fine concavo-convex shapes on the surface of the support layer.

It should be noted that, in Production Examples 4 and 5, when the support layer was produced, the drying temperature after coating the resin composition to form the coating film was made higher than the expansion start temperature (t) of the thermally expandable particles, but because of the above The drying temperature is the atmospheric temperature, so no foaming was observed in the formed support layer.

Manufacturing Example 6

As heat-expandable particles, heat-expandable microcapsules (product name "Expancel 920-40DU", expansion start temperature (t)=120° C.) manufactured by Japan Fillite Co., Ltd. were used, and the resin composition was applied to form a coating film. A support layer was produced in the same manner as in Production Example 3, except that the conditions were changed to an atmosphere temperature of 100° C. for 1 minute, and this was used as the support layer 5 .

The support layer 5 has an adhesive layer and a base material containing heat-expandable particles, and when heated to 120° C. or higher, the heat-expandable particles are expanded to generate fine irregularities on the surface of the support layer.

(Example 1)

The release film laminated on the adhesive layer (2) of the support layer 2 produced in Production Example 3 was removed, and the adhesive surface of the exposed adhesive layer (2) was The surfaces of the resin layer 1 are bonded together to obtain a releasable film/adhesive layer (1)/substrate/anchor layer/heat-expandable layer/adhesive layer (2)/thermosetting resin layer/release film in this order The anti-warp laminate with release film.

(Example 2)

The release film laminated on the adhesive layer of the support layer 1 of Production Example 2 was removed, and the adhesive surface of the exposed adhesive layer (2) was adhered to the surface of the curable resin layer 1 formed in Production Example 1. Combined, the laminated body for warpage prevention with a release film was obtained by laminating|stacking a base material/adhesive layer/thermosetting resin layer/release film in this order.

(Comparative Example 1)

The release film laminated on the second pressure-sensitive adhesive layer of the support layer 3 produced in Production Example 4 was removed, and the exposed adhesive surface of the pressure-sensitive adhesive layer (2) was allowed to adhere to the curable resin formed in Production Example 1. The surface of the layer 1 is laminated to obtain a laminate in which a heavy release film/adhesive layer (1)/substrate/anchor layer/thermally expandable layer/adhesive layer (2)/thermosetting resin layer/release film are laminated in this order. Warpage prevention laminate with release film.

(Comparative Example 2)

The release film laminated on the second pressure-sensitive adhesive layer of the support layer 4 produced in Production Example 5 was removed, and the adhesive surface of the exposed pressure-sensitive adhesive layer (2) was allowed to adhere to the curable resin formed in Production Example 1. The surface of the layer 1 is laminated to obtain a laminate in which a heavy release film/adhesive layer (1)/substrate/anchor layer/thermally expandable layer/adhesive layer (2)/thermosetting resin layer/release film are laminated in this order. Warpage prevention laminate with release film.

(Comparative Example 3)

The release film laminated on the adhesive layer (2) of the support layer 5 produced in Production Example 6 was removed, and the adhesive surface of the exposed adhesive layer (2) was The surfaces of the resin layer 1 are bonded together to obtain a releasable film/adhesive layer (1)/substrate/anchor layer/thermal expansion layer/adhesive layer (2)/thermosetting resin layer/release film in this order. Warpage prevention laminate with release film.

The laminated bodies for warpage prevention obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were measured and evaluated according to the above-mentioned measurement method and evaluation procedure. Table 1 shows the results.

[Table 1]

From the results in Table 1, in Examples 1 and 2, when the curable resin layer was cured at 130° C. for 2 hours, the peelability between the cured resin layer and the support layer was good, and the occurrence of warpage was also obtained. fully suppressed. In addition, in Examples 1 and 2, when the curable resin layer was cured at 160° C. for 1 hour, the peelability between the cured resin layer and the support layer was maintained at a level that does not pose a practical problem, and warpage was observed. occurrence has also been fully suppressed. In particular, in Example 2, the support layer was foamed to a certain extent due to curing at 160°C, and the peelability of the support layer was also slightly reduced. All of the evaluations were at the same level as the case of curing at 130°C, and a cured sealing body could be obtained in a shorter time.

On the other hand, in Comparative Examples 1 to 3, the releasability of the curable resin layer and the support layer was significantly decreased, and the interface between the support layer and the cured resin layer was not able to be peeled off.

Claims (10)

1. A laminate for preventing warping of a cured sealing body, comprising:

a curable resin layer (I) comprising a thermosetting resin layer (X1), and

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

the curable resin layer (I) has an adhesive surface having adhesiveness,

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

the warp-preventive laminate is provided with a curable resin layer (I), an adhesive layer (V) and a substrate (Y) in this order, and the adhesive surface of the curable resin layer (I) and the adhesive layer (V) are disposed on the opposite side,

the curing of the curable resin layer (I) is completed within 2 hours and the curing minimum temperature (T) of the cured resin layer (I') is formed₁) Is lower than the foaming initiation temperature of the thermally expandable particles(T₂) The temperature of (a) is set to be,

the cured sealing body is produced by sealing an object to be sealed on the adhesive surface of the curable resin layer (I).

2. The laminate for preventing warping according to claim 1, wherein the curable resin layer (I) has a minimum curing temperature (T)₁) And a foaming initiation temperature (T) of the thermally expandable particles₂) Difference between (T)₂-T₁) Is 20 to 100 ℃.

3. The laminate for preventing warping according to claim 1 or 2, wherein the curable resin layer (I) has 2 or more thermosetting resin layers (X1), and the curing minimum temperature (T) of the 2 or more thermosetting resin layers (X1)₁) Minimum value of (T)_1a) Is lower than the foaming initiation temperature (T) of the thermally expandable particles₂) The temperature of (2).

4. The laminate according to any one of claims 1 to 3, wherein the thickness of the thermosetting resin layer (X1) is 1 to 500 μm.

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 (V) is a non-expandable adhesive layer.

7. The laminate according to claim 5 or 6,

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

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

8. The laminate for preventing warping according to any one of claims 1 to 7, wherein,

the curable resin layer (I) has a1 st layer disposed on the side of the support layer (II) and a2 nd layer disposed on the side of the adhesive surface,

the 1 st layer is a thermosetting resin layer (X1-1),

the 2 nd layer is an energy ray-curable resin layer (X2).

9. A method for producing a cured sealing body by using the laminate for warpage prevention according to any one of claims 1 to 7,

the method comprises the following steps:

a step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) included in the warp-preventing laminate;

a step of coating the object to be sealed and the adhesive surface of the curable resin layer (I) on at least the peripheral portion of the object to be sealed with a thermosetting sealing material; and

and (d) a step of obtaining a cured sealed body with a cured resin layer by thermally curing the sealing material to form a cured sealed body including the object to be sealed and also thermally curing the curable resin layer (I) to form a cured resin layer.

10. A method for producing a cured sealing body by using the laminate for warpage prevention according to claim 8,

the method comprises the following steps:

a step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) included in the warp-preventing laminate;

a step of curing the energy ray-curable resin layer (X2) by irradiation with an energy ray;

a step of coating the object to be sealed and the adhesive surface of the curable resin layer (I) on at least the peripheral portion of the object to be sealed with a thermosetting sealing material; and

and a step of obtaining a cured sealed body with a cured resin layer by thermally curing the sealing material to form a cured sealed body including the object to be sealed and thermally curing the curable resin layer (I) to form a cured resin layer (I').

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