KR102576310B1 - Laminate for curing prevention of curing encapsulation body, and manufacturing method of curing encapsulation body - Google Patents

Abstract

It has a curable resin layer (I) containing a thermosetting resin layer (X1) and a support layer (II) supporting the curable resin layer (I), and the curable resin layer (I) has an adhesive surface having adhesiveness, and the support layer (II) has a base material (Y) and an adhesive layer (V), at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contains thermally expandable particles, the curable resin layer (I), and the pressure-sensitive adhesive layer ( While V) and the base material (Y) are arranged in this order, the adhesive surface of the curable resin layer (I) is arranged on the opposite side to the adhesive layer (V), and curing of the curable resin layer (I) takes 2 hours. The minimum curing temperature (T ₁ ) at which the cured resin layer (I′) is completed within 24 hours is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles, and the curable resin layer (I) is sealed on the adhesive surface. A laminate for preventing warping of a hardened encapsulant produced by encapsulating an object.

Description

Laminate for curing prevention of curing encapsulation body, and manufacturing method of curing encapsulation body

The present invention relates to a laminate for preventing curvature of a curing encapsulation body, and a method for manufacturing the curing encapsulation body.

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

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

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

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

Japanese Unexamined Patent Publication No. 2001-131507

However, according to the study of the present inventors, when a curing encapsulant is produced using the pressure-sensitive adhesive sheet described in Patent Document 1 as a sheet for temporarily fixing, when the heat-expandable particles are foamed by heating the temporarily fixed layer, the first step prior to heat-foaming It has been found that there is a possibility that the pre-cured layer may not be peeled off from the cured resin layer formed by the heating in the step. This problem tends to become more conspicuous as the size of a package such as FOWLP or FOPLP increases.

In the case of a cured encapsulant in which peeling failure has occurred, there is a risk that the encapsulated object itself, such as a semiconductor chip, may be damaged. For example, a part of the thermally expandable adhesive layer may remain on the cured resin layer or the cured resin layer itself may be damaged By doing so, adverse effects such as making it impossible to accurately perform processes such as grinding and dicing of the cured encapsulated body scheduled in the next process may occur.

In view of the above problems, the present invention has a support layer and a curable resin layer, and can fix an object to be sealed to the surface of the curable resin layer to perform a sealing process, and the cured sealing body formed by the sealing process is bent. Provision of a cured resin layer as an anti-warping layer and a curing-preventing laminate capable of preventing the occurrence of peeling defects between the curable resin layer and the support layer, and a method for producing a cured encapsulant using the curing-preventing laminate make it a task to do

As a result of repeated earnest examinations in order to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned problems could be solved by setting the adhesive force of the curable resin layer to a predetermined range, and completed the present invention.

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

[1] It has a curable resin layer (I) containing a thermosetting resin layer (X1) and a support layer (II) 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), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contains thermally expandable particles,

While the curable resin layer (I), the pressure-sensitive adhesive layer (V), and the base material (Y) are arranged in this order, the adhesive surface of the curable resin layer (I) is arranged on the opposite side to the pressure-sensitive adhesive layer (V),

The minimum curing temperature (T 1 ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I _′ ) is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles,

A laminate for preventing curvature of a cured encapsulant produced by encapsulating an object to be encapsulated on the adhesive surface of the curable resin layer (I).

[2] The above [1], wherein the difference (T ₂ - T ₁ ) between the minimum curing temperature (T 1 ) of the curable resin layer (I) and the foaming start temperature (T _{2 )} of the thermally expandable particles is 20°C to 100°C. ] The laminate for warpage prevention described in .

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

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

[5] The laminate according to any one of [1] to [4], wherein the substrate (Y) has an expandable substrate layer (Y1) containing the thermally 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 substrate (Y) has a non-expandable substrate layer (Y2) and an expandable substrate layer (Y1),

The laminate according to [5] or [6] above, wherein the support layer (II) has a non-expandable substrate layer (Y2), an expandable substrate layer (Y1), and an adhesive layer (V) in this order.

[8] The curable resin layer (I) has a first layer disposed on the support layer (II) side and a second layer disposed on the adhesive surface side,

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

Said 2nd layer is an energy-beam curable resin layer (X2), The laminated body for curvature prevention as described in any one of said [1]-[7].

[9] A method for producing a cured encapsulated body using the warp-preventing laminate according to any one of [1] to [7] above,

A step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) of the layered body for curvature prevention;

A step of covering the object to be sealed and the adhesive surface of the curable resin layer (I) of at least the periphery of the object to be sealed with a thermosetting sealing material;

The encapsulant is thermally cured to form a cured encapsulated body containing the object to be encapsulated, and the curable resin layer (I) is also thermally cured to form a cured resin layer to obtain a cured encapsulated body with a cured resin layer. A method for producing a curing encapsulated body comprising a step.

[10] A method for producing a cured encapsulated body using the warp-preventing laminate described in [8] above,

A step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) of the layered body for curvature prevention;

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

A step of covering the object to be sealed and the adhesive surface of the curable resin layer (I) of at least the periphery of the object to be sealed with a thermosetting sealing material;

The encapsulant is thermally cured to form a cured encapsulant containing the object to be encapsulated, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I′), thereby curing with the cured resin layer. A method for producing a cured sealed body with a cured resin layer, including a step of obtaining a sealed body.

According to the present invention, an object to be sealed can be fixed to the surface of the curable resin layer to perform sealing processing, and a cured resin layer as an anti-warping layer can be applied to the cured sealing body formed by the sealing processing, and further It is possible to provide a laminate for preventing warpage, which can prevent the occurrence of defective separation between the curable resin layer and the support layer, and a method for manufacturing a cured encapsulated body using the laminate for preventing warpage.

1 : is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature of the 1st aspect of this invention.
2 : is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature of the 2nd aspect of this invention.
3 : is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature of the 3rd aspect of this invention.
Fig. 4 is a cross-sectional schematic diagram of the laminate, showing the configuration of the laminate for curvature according to the fourth aspect of the present invention.
5 : is a cross-sectional schematic diagram of the said laminated body which shows the structure of the laminated body for curvature of the 5th aspect of this invention.
Fig. 6 is a cross-sectional schematic view showing a step of manufacturing a cured encapsulated body with a cured resin layer.
Fig. 7 is a cross-sectional schematic diagram showing another manufacturing step of a cured encapsulated body with a cured resin layer.

First, the terms used in this specification are explained.

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

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

In the case of a layer containing thermally expandable particles, for example, as the "expanding treatment", heat treatment may be performed at the expansion start temperature (t) of the thermally expandable particles for 3 minutes. In the case where the expandable particles expand by foaming, the expansion start temperature (t) may be referred to as the foam start temperature (T2).

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

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

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

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

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

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

In this specification, the lowest temperature at which curing of the curable resin is completed within 2 hours may be referred to as "minimum curing temperature".

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

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

[Laminate for Warpage Prevention]

The laminated body for curvature prevention of 1 aspect of this invention has the curable resin layer (I) containing the thermosetting resin layer (X1), and the support layer (II) which supports the curable resin layer (I). In addition, in the following description, the laminated body for curvature prevention may simply be called "a laminated body."

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

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

While the curable resin layer (I), the adhesive layer (V), and the base material (Y) are arranged in this order, the adhesive surface of the curable resin layer (I) is arranged on the side opposite to the adhesive layer (V). .

The minimum curing temperature (T 1 ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I _′ ) is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles.

<Configuration of laminate for warping prevention>

The structure of the laminated body for curvature prevention of this embodiment is demonstrated using drawing.

1 to 5 are cross-sectional schematic views of the laminate, showing the configuration of the laminate for curvature of the first aspect to the fifth aspect of the present invention. In addition, in the laminated body of the following 1st aspect - 5th aspect, the adhesive surface of the adhesive layer (V1) affixed to the support body which is not shown, and the 1st surface of the curable resin layer (I) (support layer ( From the viewpoint of protecting the surface of the curable resin layer (I) or the support layer (II), a release material may be further laminated on the surface opposite to II). In addition, this peeling material is peeled and removed at the time of use of the laminated body for curvature prevention.

[Laminate for Warpage Prevention of First Aspect]

As the laminate for warpage prevention of the first aspect of the present invention, laminates 1a and 1b shown in Fig. 1 are exemplified.

The laminates 1a and 1b include 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 the curable resin layer (I) It has a direct layered configuration.

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 a 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 an object to be sealed is placed, the object to be sealed can be fixed by the adhesive force.

In the laminates 1a and 1b, the adhesive surface of the pressure-sensitive adhesive layer V1 is attached to a support not shown.

In the support layer (II), at least any one of the substrate (Y) and the pressure-sensitive adhesive layer (V1) contains thermally expandable particles, and has expansibility. In the layered product 1a of Fig. 1(a), the substrate (Y) has an expandable substrate layer (Y1) containing thermally expandable particles.

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

In addition, in the laminate for warping prevention of the first aspect, in the case of using a base material (Y) having an expandable base layer (Y1) and a non-expandable base layer (Y2), as shown in Fig. 1(b), the pressure-sensitive adhesive layer It is preferable to have a configuration in which the non-expandable base layer (Y2) is laminated on the surface of (V1) and the expandable base layer (Y1) is laminated on the surface of the non-expandable base layer (Y2).

In the layered product 1a shown in FIG. 1(a), thermally expandable particles contained in the expandable substrate layer Y1 are expanded by expansion treatment by heating (hereinafter referred to as “thermal expansion treatment”). Concavo-convexity occurs on the surface of (Y), and the contact area with the cured resin layer obtained by curing the curable resin layer (I) is reduced. 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 affixed to a support (not shown). By attaching the pressure-sensitive adhesive layer (V1) to the support so as to sufficiently adhere thereto, even if a force for generating irregularities is generated on the surface of the pressure-sensitive adhesive layer (V1) side of the expandable substrate layer (Y1), the pressure-sensitive adhesive layer (V1) repels the adhesive layer (V1). Power is likely to occur. Therefore, irregularities are not easily formed on the surface of the base material (Y) on the pressure-sensitive adhesive layer (V1) side.

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

Moreover, it is also possible to make separation more easily possible in the interface P by forming the adhesive layer (V1) which the laminated body 1a has from the adhesive composition with which the adhesive force with respect to a support body increases. In the description below, the interface between 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 stress due to the thermally expandable particles to the pressure-sensitive adhesive layer (V1) side, the base material (Y) is an expandable base material layer (Y1 ) and a non-expandable substrate layer (Y2).

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

Therefore, irregularities hardly occur on the surface of the pressure-sensitive adhesive layer (V1) on the support side, and the adhesion between the pressure-sensitive adhesive layer (V1) and the support is almost unchanged before and after the thermal expansion treatment, and good adhesion can be maintained. As a result, irregularities are easily formed on the surface of the expandable base layer (Y1) on the side of the curable resin layer (I), and as a result, the interface between the expandable base layer (Y1) and the cured resin layer (I') of the support layer (II) ( In P), it becomes easily removable in batches with a slight force.

In addition, as in the laminate (1b) shown in FIG. 1(b), the expandable base material layer (Y1) and the curable resin layer (I) are directly laminated, and the curable resin layer (I) of the non-expandable base layer (Y2) It is preferable to have a structure in which the pressure-sensitive adhesive layer (V1) is laminated on the surface on the opposite side.

Further, between the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2), an adhesive layer or an anchor layer for adhering the two may be provided, or may be laminated directly.

[Laminate for warpage prevention of the second aspect]

As a laminated body for curvature of the 2nd aspect of this invention, the laminated body 2a, 2b for curvature shown in FIG. 2 is mentioned.

In the laminates 2a and 2b, the pressure-sensitive adhesive layer included in the support layer (II) includes a first pressure-sensitive adhesive layer (V1-1) and a second pressure-sensitive adhesive layer (V1-2), and the first pressure-sensitive adhesive layer (V1-1) And the base material (Y) is sandwiched by the 2nd adhesive layer (V1-2), and the adhesive surface of the 2nd adhesive layer (V1-2) has a structure laminated|stacked directly with the curable resin layer (I). Hereinafter, each adhesive layer in case the support layer (II) is provided with a plurality of adhesive layers, and the adhesive layer in case the support layer (II) is provided with a single adhesive layer are collectively referred to as the adhesive layer (V). there is

In addition, in the laminated body for curvature prevention of this 2nd aspect, the adhesive surface of the 1st adhesive layer (V1-1) is affixed to the support body which is not shown.

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

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

However, as described above, as shown in FIG. 2(b), from the viewpoint of a laminate capable of maintaining good adhesion between the first pressure-sensitive adhesive layer (V1-1) and the support before and after the thermal expansion treatment, the base material (Y) preferably has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2).

In addition, in the laminate for warpage prevention of the second aspect, when using a substrate (Y) having an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2), as shown in FIG. 2(b), the expandable substrate It is preferable to have a structure in which the second pressure-sensitive adhesive layer (V1-2) is laminated on the surface of the layer (Y1) and the first pressure-sensitive adhesive layer (V1-1) is laminated on the surface of the non-expandable substrate layer (Y2).

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

Then, the irregularities formed on the surface of the intumescent substrate layer (Y1) push the second pressure-sensitive adhesive layer (V1-2) up, and the irregularities are also formed on the adhesive surface of the second pressure-sensitive adhesive layer (V1-2). The contact area between the pressure-sensitive adhesive layer (V1-2) and the cured resin layer (I') decreases. As a result, at the interface P between the second pressure-sensitive adhesive layer (V1-2) of the support layer (II) and the cured resin layer (I'), it is possible to easily and collectively separate with a slight force.

Further, in the laminate of the present second aspect, from the viewpoint of making the laminate easily detachable en bloc with a little force at the interface (P), the expandable base layer of the base material (Y) included in the support layer (II) ( Y1) and the second pressure-sensitive adhesive layer (V1-2) are preferably directly laminated.

[Laminate for warpage prevention of the third aspect]

As the laminate for warp prevention of the 3rd aspect of this invention, the laminate for warp prevention 3 shown in FIG. 3 is mentioned.

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

In the layered product 3, the adhesive surface of the first pressure sensitive adhesive layer V1 is adhered to a support not shown.

In addition, it is preferable that the substrate (Y) included in the layered product 3 of the third aspect is constituted by a non-expandable substrate layer (Y2).

In the layered product 3 of the third aspect, the heat-expandable particles in the second pressure-sensitive adhesive layer V2, which is the expandable pressure-sensitive adhesive layer, expand through the thermal expansion treatment, and the surface of the second pressure-sensitive adhesive layer V2 has irregularities. and the contact area between the second pressure-sensitive adhesive layer (V2) and the curable resin layer (I) decreases.

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

Therefore, irregularities are easily formed on the surface of the curable resin layer (I) side of the second pressure-sensitive adhesive layer (V2) by the thermal expansion treatment, and as a result, the second pressure-sensitive adhesive layer (V2) and curing of the support layer (II) At the interface (P) of the resin layer (I'), it becomes possible to separate easily collectively with a slight force.

[Laminate for Warpage Prevention of the 4th Mode]

As a layered product for curvature of the 4th aspect of this invention, the laminated body 4 for curvature shown in FIG. 4 is mentioned.

The layered product 4 shown in FIG. 4 has a configuration in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable substrate layer (Y1), and a curable resin layer (I) are laminated in this order.

In the layered product 4, the curable resin layer (I) comprises a first thermosetting resin layer (X1-1) located on the base material (Y) side and a second thermosetting resin layer located on the opposite side to the base material (Y). It consists of curable resin layer (I) provided with (X1-2). Both the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2) are non-expandable.

Here, the surface adhesive force of the 2nd thermosetting resin layer (X1-2) is higher than that of the 1st thermosetting resin layer (X1-1). In the layered product 4, by configuring the curable resin layer (I) with two thermosetting resin layers, those of mutually different characteristics can be used. For example, a thermosetting resin layer containing a more adhesive composition is selected for the curable resin layer on the side opposite to the support layer (II), and the curable resin layer on the support layer (II) side has separability from the support layer (II) You can choose a better one than this.

[Laminate for Warpage Prevention of the Fifth Embodiment]

As a layered product for curvature of the 5th aspect of this invention, the laminated body 5 for curvature shown in FIG. 5 is mentioned.

The layered product 5 shown in FIG. 5 has a configuration in which a non-expandable pressure-sensitive adhesive layer (V1), an expandable substrate layer (Y1), and a curable resin layer (I) are laminated in this order.

In the layered product 5, the curable resin layer (I) includes a thermosetting resin layer (X1-1) located on the base material (Y) side and an energy ray curable resin layer (X2) located on the opposite side to the base material (Y). ), and a curable resin layer (I). Both the first thermosetting resin layer (X1-1) and the energy ray curable resin layer (X2) are non-expandable.

In the layered product 5, by dividing the curable resin layer (I) into an energy ray curable resin layer (X2) and a thermosetting resin layer (X1-1), those having mutually different characteristics can be used. For example, an energy curable resin layer made of an energy ray curable composition that can be easily adjusted to have relatively high adhesive strength is disposed on the opposite side of the support layer (II), and on the support layer (II) side, separability from the encapsulant described later is provided. A better thermosetting resin layer can be disposed.

[Use of Laminate for Warpage Prevention]

In the curvature-preventing laminate of the present embodiment, an object to be sealed is placed on the surface of the curable resin layer, the object to be sealed and the surface of the thermosetting resin layer at least in the periphery of the object to be sealed are coated with a sealing material, and the sealing material is It is cured and used for producing a cured encapsulated body containing an object to be encapsulated.

In addition, the specific aspect regarding the manufacture of the curing encapsulation body using the laminate for curvature prevention will be described later.

For example, after placing an object to be sealed on the adhesive surface of an adhesive laminate such as a wafer mount tape used in the manufacturing method described in Patent Document 1, the object to be sealed and the adhesive surface of its peripheral portion are coated with a sealing material, Consider a case where an encapsulant is thermally cured to produce a cured encapsulant.

When the encapsulant is thermally cured, the encapsulant is subjected to stress to shrink, but since the adhesive laminate is fixed to the support, the stress of the encapsulant is suppressed.

However, the cured encapsulant obtained by being separated from the support and the adhesive laminate cannot well suppress the stress to shrink. In the cured encapsulant after separation, since the amount of the encapsulant is different between the surface side of the side where the object to be sealed is present and the opposite surface side, a difference in shrinkage stress tends to occur. The difference in shrinkage stress causes warpage to occur in the cured encapsulant.

Further, from the viewpoint of productivity, it is common that the cured encapsulated body after heating is separated from the support body and the adhesive laminate in a state of being heated to a certain extent. Therefore, even after separation, while curing of the encapsulant proceeds, shrinkage due to natural cooling also occurs, so that the cured encapsulant is in a state where warpage is more likely to occur.

On the other hand, when using the laminated body for curvature prevention of 1 aspect of this invention, the curing sealing body which suppressed curvature effectively can be obtained for the following reasons.

In short, an object to be sealed is placed on the surface of the thermosetting resin layer of the laminate for curvature of one aspect of the present invention, covered with a sealing material, and the sealing material is thermally cured, and the thermosetting resin layer is also thermally cured at the same time. At this time, since the amount of the sealing material is small and the shrinkage stress due to curing of the sealing material is small, since the thermosetting resin layer is formed on the surface side on the side where the object to be sealed is present, the shrinkage stress due to the curing of the thermosetting resin layer is reduced. It works.

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

In addition, the thermosetting resin layer contributing to suppression of curvature of the cured encapsulated body can be made into a cured resin layer by being cured by heat.

In short, since a cured resin layer can be formed on one surface of a cured encapsulation body simultaneously by passing through the above-mentioned encapsulation process using the laminate for curvature prevention of one aspect of this invention, the cured resin layer The process for forming can be omitted, and it also contributes to the improvement of productivity.

In addition, in the laminate for curvature of one aspect 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 the curable resin layer (I ) is completed within 2 hours and the curing minimum temperature (T ₁ ) at which the cured resin layer (I′) is formed is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles. For this reason, when the said heat-expandable particle|grains expand by heating, it can prevent that peeling defect arises between curable resin layer (I) and support layer (II).

<Various physical properties of the laminate>

(Minimum Curing Temperature (T ₁ ) of Curable Resin Layer (I))

In the laminate for curvature prevention of one aspect 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 the curable resin layer (I) The minimum curing temperature (T ₁ ) at which curing is completed within 2 hours to become the cured resin layer (I′) is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles. For this reason, thermal expansion of the thermally expandable particles is suppressed while the curable resin layer is cured by heating. As a result, when the heat-expandable particles are thermally expanded, an excessive increase in the adhesion between the curable resin layer (I) and the support layer (II) can be avoided, and peeling defects between the two can be prevented from occurring.

One reason why peeling defects are suppressed is not limited to this, but is estimated as follows. During heating and hardening of the curable resin layer, when the heat-expandable particles thermally expand, irregularities are generated at the interface with the curable resin layer, and the curable resin layer is cured to strongly adhere to the irregularities. For this reason, it is considered that peelability from the cured resin layer is reduced even if the thermally expandable particles are heated and expanded after curing the curable resin layer. On the other hand, in the laminate of the present embodiment, since the thermal expansion of the thermally expandable particles is suppressed while the curable resin layer is cured by heating, the thermally expandable particles are thermally expanded after curing of the curable resin layer is completed, so that the interface with the cured resin layer is It is presumed that even if sufficient irregularities are generated, the releasability between the two is sufficiently secured.

The difference (T ₂ - T 1 ) between the minimum curing temperature (T ₁ ) of the curable resin layer (I) and the foaming start temperature (T _{2 )} of the thermally expandable particles is preferably 20 to 100°C, more preferably It is 20-90 degreeC, More preferably, it is 20-80 degreeC. By making the temperature difference T ₂ - T ₁ within the above temperature range, a sufficient temperature difference can be provided, and as a result, peeling defects can be easily suppressed, and the physical properties of the thermally expandable fine particles and the degree of freedom in material selection can be increased. .

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

In the laminate of one aspect of the present invention, from the viewpoint of improving the adhesion to the object to be sealed, the curable resin layer (I) preferably has adhesiveness on the surface (first surface) on which the object to be sealed is placed. .

The adhesive strength of the first surface of the curable resin layer (I) is obtained by attaching the first surface to a glass plate at a temperature of 70 ° C., at a temperature of 23 ° C., at a peel angle of 180 ° and at a peel rate of 300 mm / min. The value when measured by peeling is preferably 1.7 N/25 mm or more, more preferably 2.3 N/25 mm or more, still more preferably 3.0 N/25 mm or more, still more preferably 4.0 N/25 mm or more, and preferably 20 N/25 mm or less, more preferably 15 N/25 mm or less, 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), it becomes easy to prevent the object from being displaced. If the adhesive force of the 1st surface of curable resin layer (I) is 20 N/25 mm or less, selection of the material of curable resin layer (I) will become easy.

(Shear force of curable resin layer (I))

In the laminate of one aspect of the present invention, the curable resin layer (I) preferably has an appropriate shear force from the viewpoint of keeping the object to be sealed well when sealing the object. Specifically, the shear strength of the curable resin layer (I) with respect to an adherend for measurement was measured using a silicon chip (mirror surface) having a thickness of 350 μm and a size of 3 mm × 3 mm as the adherend for measurement at a temperature of 70 ° C. , the value when the mirror surface of the adherend for measurement is pressed and attached to the curable resin layer at 130 gf for 1 second, and measured at a speed of 200 µm/s, preferably 20 N/(3 mm x 3 mm) or more, more preferably 25 N/(3 mm × 3 mm), still more preferably 30 N/(3 mm × 3 mm) or more, and preferably 100 N/(3 mm × 3 mm) or less , more preferably 90 N/(3 mm x 3 mm) or less.

If the shear strength of the curable resin layer (I) to the adherend for measurement is 20 N/(3 mm × 3 mm) or more, the object to be sealed is fixed to the surface of the curable resin layer (I), and the object to be sealed by the sealing material When covering, it becomes easy to prevent the object to be sealed from being displaced or tilted due to the flow of the sealing material. Moreover, selection of the material of curable resin layer (I) becomes easy as the said shear strength is 100 N/(3 mm x 3 mm) or less.

(Adhesion of the thermosetting resin layer (X1))

In the laminate of one aspect 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/25 mm, still more preferably 0.5 to 4.0 N/25 mm.

Like the layered product 4 shown in FIG. 4, when it has a 1st thermosetting resin layer (X1-1) and a 2nd thermosetting resin layer (X1-2), it is preferable that each has the said 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 fixed to the first surface of the curable resin layer (I) more reliably. there is.

(Adhesion of Energy Ray Curable Resin Layer (X2))

In the laminate of one aspect of the present invention, the adhesive strength 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/25 mm, more preferably from 0.4 to 6.0 N/25 mm, even more preferably from 0.5 to 4.0 N/25 mm.

(Adhesive strength of the pressure-sensitive adhesive layer (V))

In the laminate of one aspect of the present invention, the adhesive force of the pressure-sensitive adhesive layer (V) (first pressure-sensitive adhesive layer (V1) and second pressure-sensitive adhesive layer (V2)) of the support layer (II) 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, even more preferably 0.4 to 6.0 N/25 mm, still more preferably 0.5 to 4.0 N/25 mm am. In the following description, regardless of whether the pressure-sensitive adhesive layer is single or plural, the pressure-sensitive adhesive layer positioned on the curable resin layer (I) side is the first pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer positioned on the opposite side to the curable resin layer is provided. 2 It may be called an adhesive layer.

When 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 first pressure sensitive adhesive layer (V1-1) or (V1) and the adhesive strength of the second pressure-sensitive adhesive layer (V1-2) or (V2) are preferably within the above ranges, respectively. From a viewpoint, it is more preferable that the adhesive force of the support body and the 1st adhesive layer (V1-1) or (V1) affixed is higher than the adhesive force of the 2nd adhesive layer (V1-2) or (V2).

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

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

First, the laminate for curvature prevention provided with curable resin layer (I) and support layer (II) is cut to 25 mm width x 250 mm length (MD direction is 250 mm), and a primary sample is manufactured. Moreover, as a to-be-adhered body, a glass plate (3 mm (JIS R3202 product) of float plate glass by Yuko Corporation) is prepared. Using a laminator (VA-400 type manufactured by Taisei Laminator Co., Ltd.), a glass plate is affixed so as to directly contact the first surface of the curable resin layer (I) to obtain a test piece. At this time, the roller temperature is made into 70 degreeC and the sticking speed|rate is made into conditions of 0.2 m/min. After leaving the test piece obtained in this way for 24 hours in an environment of 23°C and 50% RH (relative humidity), under the same environment, based on JIS Z 0237: 2000, a tensile load measuring instrument (A&D Manufacture, Tensilon), the test piece was peeled 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 was measured, and the measured value of the curable resin layer (I) It is taken as the adhesive force of the 1st surface.

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

In this specification, the shear force of curable resin layer (I) is measured in the following procedure.

First, a 350 μm-thick silicon chip with a 3 mm x 3 mm mirror surface is used as an adherend for measurement. Then, the mirror surface of the adherend for measurement was pressed at 130 gf for 1 second at a temperature of 70° C. to the first surface of the curable resin layer (I) of each laminate obtained in each of Examples and Comparative Examples described below, attach Then, the shear force is measured at a speed of 200 μm/s using a universal bond tester (DAGE4000, manufactured by Nordson Advanced Technologies).

(Measurement of adhesive force of adhesive layer (V), thermosetting resin layer (X1), energy ray curable resin layer (X2))

An adhesive tape (manufactured by Lintec Corporation, product name “PL Shin”) is laminated on the surface of the adhesive layer (V), the thermosetting resin layer (X1), or the energy ray curable resin layer (X2) formed on the peeling film.

Then, the surface of the pressure-sensitive adhesive layer (V), the thermosetting resin layer (X1), or the energy ray-curable resin layer (X2) exposed by peeling off the release film is a glass plate as an adherend (float plate glass 3 mm (JIS manufactured by Yuko Corporation) It was attached to R3202 product)). At this time, the sticking temperature of the pressure-sensitive adhesive layer (V) was 23°C, and the sticking temperature of the thermosetting resin layer (X1) and the energy ray-curable resin layer (X2) was 70°C. Then, after leaving the glass plate to which each layer was attached was left still for 24 hours in an environment of 23° C. and 50%RH (relative humidity), under the same environment, based on JIS Z 0237: 2000, by a 180° peeling method , The adhesive force in 23 degreeC is increased by peeling the adhesive layer (V), the thermosetting resin layer (X1), or the energy ray-curable resin layer (X2) together with an adhesive tape from the said glass plate at a tensile speed of 300 mm/min. Measure.

(Peel force before expansion treatment (F ₀ ))

Prior to curing of the curable resin layer (I) and before the expansion treatment, from the viewpoint of sufficiently fixing the object to be sealed and not adversely affecting the sealing operation, it is preferable that the adhesion between the support layer (II) and the curable resin layer (I) is high. do.

From the above viewpoint, in the laminate of one aspect of the present invention, the interface (P) between the support layer (II) and the curable resin layer (I) before the curable resin layer (I) is cured and before the thermal expansion treatment is performed. ), the peel force (F ₀ ) at the time of separation is preferably 100 mN/25 mm or more, more preferably 130 mN/25 mm or more, still more preferably 160 mN/25 mm or more, and Preferably it is 50,000 mN/25 mm or less.

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

(Measurement of Peel Force (F ₀ ))

After the laminate 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 passed through an adhesive layer through a glass plate (Yukou Corporation float plate glass 3 mm ( Attached to JIS R3202 product)). Further, an adhesive tape (manufactured by Lintec Co., Ltd., product name "PL Shin") is affixed to the first surface side of the laminate. Next, the edge of the glass plate to which the laminate was attached is fixed to the lower chuck of a universal tensile tester (manufactured by Orientec Co., Ltd., product name "Tensilon UTM-4-100").

Subsequently, the end of the adhesive tape affixed to the curable resin layer (I) of the laminate with the upper chuck of the universal tensile tester so as to peel at the interface (P) between the support layer (II) and the curable resin layer (I) of the laminate fix it Then, under the same environment as above, based on JIS Z 0237: 2000, the curable resin layer (I) and the adhesive tape were separated from the interface (P) by the 180 ° peeling method at a tensile speed of 300 mm / min. The peeling force measured at the time of peeling from II) is referred to as "peeling force (F ₀ )".

(Peel force after expansion treatment (F ₁ ))

In the laminate of one embodiment of the present invention, the interface (P) of the support layer (II) and the curable resin layer (I) or the cured resin layer (I') obtained by curing the curable resin layer (I) is formed by expansion treatment. , it becomes easily detachable collectively with a little force.

Here, in the laminate of one aspect of the present invention, after the curable resin layer (I) is cured to form the cured resin layer (I'), the support layer (II) and the cured resin layer (I') are formed by expansion treatment. As the peel force (F ₁ ) at the time of separation at the interface (P) of, usually 2,000 mN / 25 mm or less, preferably 1,000 mN / 25 mm or less, more preferably 500 mN / 25 mm or less, more It is preferably 150 mN/25 mm or less, more preferably 100 mN/25 mm or less, even more preferably 50 mN/25 mm or less, and most preferably 0 mN/25 mm or less.

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

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

(Measurement of Peel Force (F ₁ ))

The support layer (II) side of the laminate is affixed to a glass plate (3 mm float plate glass manufactured by Yuko Corporation (JIS R3202 product)) with an adhesive layer interposed therebetween. Then, curable resin layer (I) is hardened by heating the said glass plate and laminated body at 130 degreeC for 2 hours, and cured resin layer (I') is formed. When the curable resin layer (I) includes the energy ray-curable resin layer (X2) as in the laminate 4 of FIG. 4 , after thermal curing of the thermosetting resin layer (X1-1), the energy ray-curable water The energy ray-curable resin layer (X2) is cured by irradiating an energy ray capable of curing the stratum layer (X2) (in the case of ultraviolet rays, irradiation with an illuminance of 215 mW/cm 2 and a light amount of 187 mJ/cm 2 three times).

Next, the heat-expandable particles included in the supporting layer (II) are expanded. Specifically, the glass plate to which the laminate is stuck is heated at 240°C for 3 minutes to expand the thermally expandable particles in the expandable substrate layer (Y1) or expandable pressure-sensitive adhesive layer (V2) of the laminate. After that, an adhesive tape (manufactured by Lintec Co., Ltd., product name "PL Shin") was attached to the first surface side of the laminate, and the same as in the measurement of the peel force (F ₀ ) described above, under the above conditions, the support layer (II) and the peeling force measured when peeling at the interface (P) of the cured resin layer (I') is referred to as "peeling force (F ₁ )".

In addition, in the measurement of the peel force (F ₁ ), when fixing the end of the adhesive tape attached to the cured resin layer (I') of the laminate with the upper chuck of the universal tensile tester, the interface (P) In the case where the cured resin layer (I') is completely separated and the fixing for measurement is not performed, the measurement is terminated, and the peeling force (F ₁ ) at that time is set to "0 mN/25 mm".

(Probe tack value of substrate (Y))

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

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

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

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

(Measurement of probe tack value)

After cutting the substrate to be measured into a square with a side of 10 mm, what was left still for 24 hours in an environment of 23°C and 50% RH (relative humidity) was used as a test sample. In an environment of 23°C and 50% RH (relative humidity), the probe tack value on the surface of the test sample was measured according to JIS Z0237: 1991 using a tacking tester (manufactured by Nippon Special Instrument Co., Ltd., product name "NTS-4800"). Measure according to Specifically, a stainless steel probe having a diameter of 5 mm is brought into contact with the surface of the test sample at a contact load of 0.98 N/cm for 1 second, and then the probe is separated from the surface of the test sample at a speed of 10 mm/sec. The force required for this is measured, and the obtained value is used as the probe tack value of the test sample.

Next, each layer constituting the laminate for curvature of one aspect of the present invention is described.

<Curable Resin Layer (I)>

The laminated body for curvature prevention of 1 aspect of this invention has curable resin layer (I) containing the thermosetting resin layer (X1).

By curing the curable resin layer (I), the difference in shrinkage stress between the two surfaces of the cured encapsulant accompanying curing of the encapsulant is reduced, contributing to suppression of warpage that may occur in the obtained cured encapsulation body.

Curable resin layer (I) turns into cured resin layer (I') by hardening. The cured resin layer (I') is formed on one surface of the resulting cured sealed body.

As described above, the minimum curing temperature (T ₁ ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I′) is caused by the foaming of the thermally expandable particles included in the support layer (II). It is lower than the starting temperature (T ₂ ). Such physical properties are mainly brought about by 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 Pa from the viewpoint of making the laminate for curing prevention capable of producing a cured sealed body having a flat surface by suppressing warpage. 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 It is preferably 1.0 × 10 ¹² Pa or less, more preferably 5.0 × 10 ¹¹ Pa or less, and still more preferably 1.0 × 10 ¹¹ Pa or less.

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

First, when the curable resin layer (I) is laminated to a thickness of 200 μm, and then curing is substantially completed (time when the exothermic peak disappears at 130° C. in measurement using a differential scanning calorimetry device) harden until In the case of the thermosetting resin layers (X1), (X1-1), and (X1-2), they are placed in an oven in an air atmosphere, and the resin is heated at 130 ° C. for 2 hours to thermally cure the thermosetting resin layer having a thickness of 200 μm. let it In the case of including the energy ray-curable resin layer (X2) and the thermosetting resin layer (X1-1), energy rays are irradiated (in the case of ultraviolet rays, irradiation with an illuminance of 215 mW/cm 2 and a light amount of 187 mJ/cm 2 three times), 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 device (manufactured by TA Instruments, product name "DMAQ800"), 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 Then, the storage modulus (E') of the formed cured resin layer at 23°C is measured.

The 1st surface which is the surface of the curable resin layer (I) on the opposite side to the support layer has adhesiveness. And, as described above, the adhesive strength is obtained by attaching the first surface to a glass plate at a temperature of 70 ° C., peeling the curable resin layer at a temperature of 23 ° C., a peeling angle of 180 °, and a peeling rate of 300 mm / min. It is a value at the time of measurement, Preferably it is 1.7 N/25 mm or more.

In addition, in the present specification, in the measurement of the adhesive force of the curable resin layer (I), "attached at a temperature of 70 ° C.", by pressing the laminate against the glass plate with a pressurizing body such as a pressure roller having a heating temperature of 70 ° C. , It means sticking a laminated body to a glass plate.

Although an object to be sealed is placed on the first surface of the curable resin layer (I), since the surface of the curable resin layer (I) has the above adhesiveness, adhesion to the object to be sealed is improved, and objects to be sealed such as semiconductor chips are When placing on the first surface, the object to be sealed is prevented from inclining or the object to be sealed being displaced from the intended position with respect to the curable resin layer (I) after the object is placed.

In addition, the shear strength of the curable resin layer (I) with respect to the adherend for measurement was 130 at a temperature of 70 ° C. using a silicon chip (mirror surface) having a thickness of 350 μm and a size of 3 mm × 3 mm as the adherend for measurement. It is a value when the mirror surface of the adherend for measurement is pressed and adhered to the curable resin layer for 1 second at gf and measured at a speed of 200 µm/s, preferably 20 N/(3 mm × 3 mm) or more. .

The adhesive strength of the first surface of the curable resin layer (I) and the shear force of the curable resin layer (I) to the adherend for measurement are components of the thermosetting resin composition or energy ray curable resin composition constituting the curable resin layer (I). It can be set as the said numerical range by adjusting the kind or compounding ratio of. The adhesive force and shear force change depending on the components and compounding ratio of the resin composition, and the shear force also changes depending on the structure of the entire layer of the curable resin layer (I). It becomes easy to set it as a high value by using as a component, using an epoxy resin as a thermosetting component, or using a coupling agent. Moreover, about shear force, it becomes easy to set it as a high value by increasing content of an inorganic filler or a crosslinking agent, for example.

The thickness of the curable resin layer (I) is preferably 1 to 500 μm, more preferably 5 to 300 μm, even 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 layer (X1), (X1-1), and (X1-2) may be collectively referred to as the thermosetting resin layer (X1).

The curable resin composition may further contain at least one selected from a coloring agent (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 using it as the laminated body for curvature prevention which can manufacture the curing sealing body which suppresses warpage and has a flat surface.

In the thermosetting resin layer (X1), the curing of the thermosetting resin layer (X1) itself is completed within 2 hours so that the minimum curing temperature (T ₁ ) of the curable resin layer (I) satisfies the above-mentioned relationship. It is preferable that the minimum curing temperature (T ₁ ) of the cured resin layer (I′) is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles included in the supporting layer (II). The minimum curing temperature (T ₁ ) of the thermosetting resin layer (X1) is preferably 20° C. or higher, more preferably 25° C. or higher, still more preferably 30° C. or higher relative to the foaming start temperature (T ₂ ) of the thermally expandable particles. lower than °C.

In order to lower the minimum curing temperature, a curing accelerator may be added, the amount of the curing accelerator or crosslinking agent may be increased, or a monomer that is more easily crosslinked may be selected.

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

As in the thermosetting resin layers (X1-1) and (X1-2), when the thermosetting resin layer (X1) includes a plurality of layers, the total thickness of the thermosetting resin layer (X1) is equal to the thickness of the curable resin layer (I). It should be within the numerical range. Further, the thickness of the thinnest layer among these layers is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more of the thickness of the thickest layer.

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

As the thermosetting resin layer (X1), one whose curing start temperature is lower than the expansion start temperature of the thermally expandable particles is used. The starting temperature of curing of the thermosetting resin layer (X1) is preferably 5°C or lower, more preferably 10°C or lower, still more preferably 20°C or lower than the expansion starting temperature of the thermally expandable particles.

(Polymer component (A))

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

When the thermosetting resin composition contains the polymer component (A), the thermosetting resin layer formed has flexibility and film-forming properties, and the property retention of the laminate can be improved.

The mass 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 150 However, it is more preferably 200,000 to 1,000,000.

The content of component (A) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 50% by mass, based on the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. It is 30 mass %.

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

These polymer components (A) may be used independently or may use 2 or more types together.

In addition, in this specification, the acrylic polymer having an epoxy group and the phenoxy resin having an epoxy group have thermosetting properties, but if these are compounds having a mass average molecular weight of 20,000 or more and having at least one repeating unit, the polymer It shall be included in the concept of component (A).

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

The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100% by mass, more 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. is 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass.

(Acrylic Polymer (A1))

The mass 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, More preferably, it is 250,000 to 1,000,000.

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

Examples of the acrylic polymer (A1) include a polymer containing an alkyl (meth)acrylate as a main component, and specifically, an alkyl (meth)acrylate (a1') having an alkyl group of 1 to 18 carbon atoms (hereinafter referred to as "monomer"). (a1')") is preferably an acrylic polymer containing a structural unit (a1) derived from, and a functional group-containing monomer (a2') together with the structural unit (a1) (hereinafter also referred to as "monomer (a2')" An acrylic copolymer containing the structural unit (a2) derived from) is more preferable.

An acrylic polymer (A1) may be used independently or may use 2 or more types together.

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

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

These monomers (a1') may be used independently or may use 2 or more types together.

From the viewpoint of improving the reliability of a cured encapsulated body with a cured resin layer, which is produced using a laminate for warpage prevention, the monomer (a1') contains an alkyl (meth)acrylate having an alkyl group of 1 to 3 carbon atoms. It is preferable, and it is more preferable that methyl (meth)acrylate is included.

From the above viewpoint, the content of the structural unit (a11) derived from an alkyl (meth)acrylate having an alkyl group of 1 to 3 carbon atoms is preferably It is 1-80 mass %, More preferably, it is 5-80 mass %, More preferably, it is 10-80 mass %.

Further, the monomer (a1') preferably contains an alkyl (meth)acrylate having an alkyl group of 4 or more carbon atoms, more preferably contains an alkyl (meth)acrylate having an alkyl group of 4 to 6 carbon atoms, and butyl It is more preferable to include (meth)acrylate.

From the above viewpoint, the content of the structural unit (a12) derived from an alkyl (meth)acrylate having an alkyl group having 4 or more (preferably 4 to 6, more preferably 4) carbon atoms is the total amount of the acrylic polymer (A1) It is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and even more preferably 10 to 60% by mass relative to the structural unit (100% by mass).

The content of the structural unit (a1) is preferably 50% by mass or more, more preferably 50 to 99% by mass, still more preferably 55 to 99% by mass, based on all the structural units (100% by mass) of the acrylic polymer (A1). It is 90 mass %, More preferably, it is 60-90 mass %.

As the monomer (a2'), at least one selected from hydroxy group-containing monomers and epoxy group-containing monomers is preferable.

In addition, monomer (a2') may be used independently and may use 2 or more types together.

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

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

Examples of the epoxy-containing monomer include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 3-epoxy epoxy group-containing (meth)acrylates such as cyclo-2-hydroxypropyl (meth)acrylate; Glycidyl crotonate, allyl glycidyl ether, etc. are mentioned.

Among these, as an epoxy-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% by mass, more preferably 5 to 45% by mass, still more preferably 10% by mass, based on all the structural units (100% by mass) of the acrylic polymer (A1). to 40% by mass, more preferably 10 to 30% by mass.

Further, the acrylic polymer (A1) may have a structural unit derived from a monomer other than the aforementioned structural units (a1) and (a2) within a range not impairing the effects of the present invention.

Examples of other monomers include vinyl acetate, styrene, ethylene, and α-olefins.

(thermosetting component (B))

The thermosetting component (B) is a compound having a mass average molecular weight of less than 20,000, which serves to thermally cure the formed thermosetting resin layer to form a hard cured resin layer.

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

As the thermosetting component (B), it is preferable to include an epoxy compound (B1), which is a compound having an epoxy group, and a heat curing agent (B2), from the viewpoint of making a laminate for curing prevention capable of producing a cured encapsulated body having a flat surface by suppressing warpage. And it is more preferable to further include a hardening accelerator (B3) together with the epoxy compound (B1) and the heat curing agent (B2).

Examples of the epoxy compound (B1) include polyfunctional epoxy resins, bisphenol A diglycidyl ether and its hydrogenated products, ortho cresol novolak epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, In molecules such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenylene skeleton type epoxy resins, epoxy compounds having two or more functional groups and having a mass average molecular weight of less than 20,000 are exemplified.

Epoxy compound (B1) may be used independently or may use 2 or more types together.

The content of the epoxy compound (B1) is preferably based on 100 parts by mass of the polymer component (A) contained in the thermosetting resin composition, from the viewpoint of making a laminate for curing prevention capable of producing a cured sealed body having a flat surface by suppressing warpage. 1 to 500 parts by mass, more preferably 3 to 300 parts by mass, even more preferably 10 to 150 parts by mass, still more preferably 20 to 120 parts by mass.

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

As the heat curing agent, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule is preferable.

Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. 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 , an amino group is more preferred.

Examples of the phenolic thermosetting agent having a phenolic group include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-type phenolic resins, xylock-type phenolic resins, and aralkylphenol resins. there is.

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

These thermosetting agents (B2) may be used independently or may use 2 or more types together.

The content of the heat curing agent (B2) is preferably from 0.1 to 500 with respect to 100 parts by mass of the epoxy compound (B1), from the viewpoint of producing an adhesive laminate capable of producing a cured sealed body with a cured resin layer having a flat surface by suppressing warpage. parts by mass, more preferably 1 to 200 parts by mass.

The curing accelerator (B3) is a compound having a function of increasing the speed of thermal curing 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 -Imidazoles such as hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate and triphenylphosphine tetraphenyl borate; and the like.

These hardening accelerators (B3) may be used independently or may use 2 or more types together.

The content of the curing accelerator (B3) is preferably, with respect to 100 parts by mass of the total amount of the epoxy compound (B1) and the thermosetting agent (B2), from the viewpoint of making a laminate for curing prevention capable of producing a cured sealed body having a flat surface by suppressing warpage. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, still more preferably 0.3 to 4 parts by mass.

(colorant (C))

The thermosetting resin composition used in one aspect of the present invention may further contain a coloring agent (C).

When the thermosetting resin layer formed from the thermosetting resin composition containing the colorant (C) is thermally cured to obtain a cured resin layer, the effect of making it easy to determine the presence or absence of the cured resin layer by appearance can be imparted, and , it is possible to impart an effect such as shielding infrared rays generated from peripheral devices and preventing malfunction of objects to be sealed (semiconductor chips, etc.).

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

As the dye, it is possible to use any dyes such as acid dyes, reactive dyes, direct dyes, disperse dyes, and cationic dyes, for example.

In addition, the pigment is not particularly limited, and can be appropriately selected and used from known pigments.

Among these, a black pigment is preferable from the viewpoint of good shielding properties of electromagnetic waves and infrared rays.

Examples of the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, and activated carbon, but carbon black is preferable from the viewpoint of enhancing the reliability of the semiconductor chip.

In addition, these coloring agents (C) may be used independently or may use 2 or more types together.

However, in the thermosetting resin composition used in one aspect of the present invention, the content of the coloring agent (C) is preferably less than 8% by mass relative to the total amount (100% by mass) of active ingredients in the thermosetting resin composition.

If the content of the colorant (C) is less than 8% by mass, it is possible to obtain a laminate for warping prevention in which the presence or absence of cracks on the surface of the chip and chipping can be visually confirmed.

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

In addition, from the viewpoint of expressing the effect of shielding infrared rays and the like in the cured resin layer formed by thermally curing the formed thermosetting resin layer, the content of the colorant (C) is the total amount of the active ingredients of the thermosetting resin composition (100% by mass) , it 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 aspect 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 adhesiveness with the object to be sealed at the time of mounting an object to be sealed. Moreover, the cured resin layer formed by thermosetting the thermosetting resin layer can also improve water resistance without impairing heat resistance.

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

As the silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 -(methacryloxypropyl)trimethoxysilane, 3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3- Aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, Bis (3-triethoxysilylpropyl) tetrasulfane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc. are mentioned.

These coupling agents (D) may be used independently or may use 2 or more types together.

The molecular weight of the coupling agent (D) is preferably 100 to 15,000, more preferably 125 to 10,000, still more preferably 150 to 5,000, still more preferably 175 to 3,000, 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, still more preferably 0.10 to 100% by mass, based on the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. It is 4 mass %, More preferably, it is 0.15-2 mass %.

(Inorganic filler (E))

The thermosetting resin composition used in one aspect of the present invention preferably further contains an inorganic filler (E) from the viewpoint of making a laminate for curing prevention capable of producing a cured sealed body having a flat surface by suppressing warpage.

By making the thermosetting resin layer formed from the thermosetting resin composition containing the inorganic filler (E), when thermally curing the encapsulant, the heat of the thermosetting resin layer is reduced so that the difference in shrinkage stress between the two surfaces of the cured encapsulant is reduced. The degree of hardening can be adjusted. As a result, it becomes possible to manufacture a cured encapsulated body having a flat surface with curvature suppressed.

In addition, the thermal expansion coefficient of the cured resin layer formed by thermally curing the formed thermosetting resin layer can be adjusted to an appropriate range, and the reliability of the object to be sealed can be improved. Moreover, the moisture absorption rate of the said 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, and the like; can be heard

These inorganic fillers (E) may be used independently or may use 2 or more types together.

Among these, silica or alumina is preferable from the viewpoint of making a laminate for warpage prevention capable of producing a cured sealed body having a flat surface by suppressing warpage.

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 thermally curing the formed thermosetting resin layer. More preferably, it is 0.3 to 30 μm, particularly preferably 0.5 to 10 μm.

The content of component (E) is preferably 25% relative to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition from the viewpoint of making a laminate for curing prevention capable of producing a cured sealed body having a flat surface by suppressing warpage. to 80% by mass, more preferably 30 to 70% by mass, even more preferably 40 to 65% by mass, still more preferably 45 to 60% by mass.

(other additives)

The thermosetting resin composition used in one aspect of the present invention may further contain additives other than components (A) to (E) described above within a range not impairing the effects of the present invention.

As another additive, a crosslinking agent, a leveling agent, a plasticizer, an antistatic agent, an antioxidant, an ion trapping agent, a gettering material, a chain transfer agent, etc. are mentioned, for example.

However, the total content of other additives other than components (A) to (E) is preferably 0 to 20% by mass, more preferably 0 to 20% by mass, based on the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. It is 0-10 mass %, More preferably, it is 0-5 mass %.

When the curable resin layer (I) is composed of a single layer of the thermosetting resin layer (X1) as shown in Figs. 1, 2 and 3, the thermosetting resin layer (X1) of the single layer has the above structure. As shown in Fig. 4, the curable resin layer (I) is located on the opposite side (first surface side) of the first thermosetting resin layer (X1-1) located on the support layer (II) side and the support layer (II) In the case of having two or more thermosetting resin layers (X1), as in the case of including the second thermosetting resin layer (X1-2), the minimum curing temperature in the two or more thermosetting resin layers (X1) ( It is preferable that the minimum value (T _1a ) of T ₁ ) is lower than the foaming start temperature (T ₂ ) of the heat-expandable particles included in the supporting layer (II). Even if the minimum curing temperatures (T ₁ ) of the plurality of layers included in the thermosetting resin layer (X1) are different, the curable resin layer exhibiting their minimum value (T _1a ) is higher than the foaming start temperature (T ₂ ) of the thermally expandable particles. Since it has a low-temperature curing minimum temperature (T ₁ ), expansion of the thermally expandable particles is suppressed during curing of the curable resin layer, and excessive adhesion with the curable resin layer is prevented. Among the plurality of layers constituting the thermosetting resin layer (X1), when the layer having T _1a is disposed most on the support layer side, this effect is remarkable, but when other layers among the plurality of layers exhibit (T _1a ) Even in this case, the peelability of the cured resin layer (I') and the support layer (II) can be prevented from being damaged. One reason for this is presumed to be that, since the other layer is cured while the expansion of the thermally expandable particles is suppressed, when the thermally expandable particles are expanded later, the presence of the other layer after curing increases the peelability.

Moreover, it is good also considering the 1st thermosetting resin layer (X1-1) and the 2nd thermosetting resin layer (X1-2) as mutually different adhesive force, for example. In this case, the second thermosetting resin layer (X1-2) located on the first surface side is the second thermosetting resin layer (X1-2) having a higher surface adhesive force than the first thermosetting resin layer (X1-1). It is desirable to do In addition, as a method for increasing the adhesive force of the second thermosetting resin layer higher than that of the first thermosetting resin layer, for example, a coupling agent is changed to generate a higher adhesive force, and the addition ratio of the inorganic filler is selected. can be reduced, 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 to increase the former. 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 include a thermosetting resin layer (X1-1) and an energy ray curable resin layer (X2).

In this case, the curable resin layer (I) includes a first layer located on the support layer side and a second layer located on the first surface side, and the first layer is a thermosetting resin layer (X1-1), It is preferable that the said 2nd layer is an energy ray-curable resin layer (X2). The thermosetting resin layer (X1-1) has the structure described above.

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

Compared with the thermosetting resin layer, the energy ray-curable resin layer (X2) is easier to adjust to increase the adhesive force, so it is easier to fix the object to be sealed to the first surface more reliably.

By irradiating an energy ray to the energy ray-curable resin layer using such an energy ray-curable pressure-sensitive adhesive composition and curing it, cure shrinkage of the curable resin layer can be easily prevented from occurring during thermal curing of the encapsulant described later, It becomes advantageous to prevent warpage from occurring in the curing encapsulation body. In addition, when a heat-curable pressure-sensitive adhesive composition is heated at a high temperature, it softens mainly in the initial stage of curing, and thus may cause chip misalignment. Since it does not become, it is possible to avoid the occurrence of chip displacement accompanying hardening.

Moreover, although ultraviolet rays, electron beams, radiation, etc. are mentioned as an energy beam, an ultraviolet-ray is preferable from a viewpoint of the availability of a curable resin composition and the ease of handling of an energy beam irradiation apparatus.

The energy ray-curable pressure-sensitive adhesive composition may be a composition containing an energy ray-curable pressure-sensitive adhesive resin obtained by introducing a polymerizable functional group such as a (meth)acryloyl group or a vinyl group into the side chain of the above-mentioned pressure-sensitive adhesive resin. may be a composition containing a monomer or oligomer having

Moreover, it is preferable to further contain a photoinitiator in these compositions.

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

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

The content of the photopolymerization initiator is preferably from 0.01 to 10 parts by mass, more preferably from 0.03 to 5 parts by mass, based on 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. It is preferably 0.05 to 3 parts by mass, particularly preferably 0.1 to 3 parts by mass.

The shear force of the entire curable resin layer (I) may be increased 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).

<Support layer (II)>

The support layer (II) of the laminate of one aspect of the present invention includes a base material (Y) and an adhesive layer (V), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contains thermally expandable particles. desirable. As described above, the support layer (II) is a layer separated from the curable resin layer (I) by expansion treatment or the like, and serves as a temporarily fixed layer.

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

- 1st aspect of support layer (II): The support layer (II) provided with the base material (Y) which has the expandable base material layer (Y1) containing thermally expandable particle|grains.

2nd aspect of support layer (II): The 2nd adhesive layer (V2) which is an expandable adhesive layer containing thermally expandable particle|grains is formed on one surface of the base material (Y), and on the other surface, a non-expandable adhesive layer is formed. The support layer (II) which has the 1st adhesive layer (V1) which is an adhesive layer.

(First aspect of support layer (II))

As a first aspect of the support layer (II), as shown in Figs. 1 to 2, 4 and 5, the base material (Y) includes an expandable base layer (Y1) containing thermally expandable particles.

It is preferable that the pressure-sensitive adhesive layer (V) is a non-expandable pressure-sensitive adhesive layer from the viewpoint of enabling easy collective separation at the interface (P) with a slight force.

Specifically, in the support layer (II) included in the laminates 1a and 1b shown in Fig. 1, the laminate 4 shown in Fig. 4, and the laminate 5 shown in Fig. 5, the pressure-sensitive adhesive layer (V1) It is preferable that this is a non-expandable adhesive layer.

Moreover, in the support layer (II) which the layered product 2a, 2b shown in FIG. 2 has, both the 1st adhesive layer (V1-1) and the 2nd adhesive layer (V1-2) are non-expandable adhesive layers. It is desirable to be

As in the first aspect of the support layer (II), when the base material (Y) has the expandable base layer (Y1), the pressure-sensitive adhesive layer (V1) does not need to have expandability, and the composition, configuration and process for imparting expandability not bound As a result, when designing the pressure-sensitive adhesive layer (V1), for example, it is possible to prioritize desired performance other than expansibility, such as performance such as adhesiveness, productivity, and economy, so that the degree of freedom in designing the pressure-sensitive adhesive layer (V) is improved. can make it

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, still more preferably is 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, and still more preferably It is preferably 5 to 30 μm.

In addition, in this specification, for example, as shown in FIG. 2, when support layer (II) has several adhesive layers, said "thickness of adhesive layer (V)" is the thickness of each adhesive layer (In FIG. 2, each thickness of the 1st adhesive layer (V1-1) and the 2nd adhesive layer (V1-2)) is meant.

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

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

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

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

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

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

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

(Second aspect of support layer (II))

As the second aspect of the support layer (II), as shown in Fig. 3, the first pressure-sensitive adhesive layer (V1), which is a non-expandable pressure-sensitive adhesive layer, is disposed on one surface of the substrate (Y), and on the other surface, and those in which a second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer containing heat-expandable particles, is disposed.

In the second aspect of the support layer (II), the second pressure-sensitive adhesive layer (V2), which is an expandable pressure-sensitive adhesive layer, and the curable resin layer (I) directly contact each other.

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

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

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

In the second aspect 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, still more preferably 0.2 to 3 μm.

Hereinafter, after explaining the heat-expandable particles that can be contained in any layer constituting the support layer (II), the expandable base layer (Y1), the non-expandable base layer (Y2), and the pressure-sensitive adhesive layer ( V) is described in detail.

(thermal expansible particles)

The expandable particle used in one aspect of the present invention is not particularly limited as long as it expands itself by heating to form irregularities on the adhesive surface of the pressure-sensitive adhesive layer (V2) and reduce the adhesive force with the adherend. .

Thermally expandable particles are superior in versatility and handling properties compared to energy ray expandable particles or the like that expand by energy ray irradiation.

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

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

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

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

The thermally expansible particles used in one aspect of the present invention may be particles that do not expand when curing the encapsulant and have an expansion start temperature (t) higher than the curing temperature of the encapsulant. Specifically, the expansion start temperature (t) ) is preferably a thermally expandable particle adjusted to 60 to 270°C.

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

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

The thermally expandable particles are preferably a microencapsulated foaming agent composed of an outer shell made of a thermoplastic resin and an encapsulated component contained in the outer shell and vaporized when heated to a predetermined temperature.

Examples of the thermoplastic resin constituting the outer shell of the microencapsulation foaming agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, and polyvinyl chloride. Leaden, polysulfone, etc. are mentioned.

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

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

The expansion start temperature t of the thermally expandable particles can be adjusted by appropriately selecting the type of the encapsulated component, and is adjusted so as to be higher than the minimum curing temperature T ₁ of the curable resin layer (I).

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

<Intumescent base layer (Y1)>

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

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

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

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

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

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

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

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

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

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

The storage elastic modulus (E′) (t) of the expandable substrate layer (Y1), which is specified in the requirement (1), is preferably 9.0 × 10 ⁶ Pa or less, more preferably 8.0 × 10 ⁶ Pa or less, from the above viewpoint. , more preferably 6.0 × 10 ⁶ Pa or less, still more preferably 4.0 × 10 ⁶ Pa or less.

In addition, the flow of the expanded thermally expandable particles is suppressed to improve the shape retention of concavo-convex formed on the surface of the support layer (II) on the side where the curable resin layer (I) is laminated, and a slight force is applied at the interface (P). From the viewpoint of making separation possible more easily, the storage modulus (E') (t) of the expandable base layer (Y1) specified in the requirement (1) is preferably 1.0 × 10 ³ Pa or more, more preferably is 1.0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

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

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

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

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

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

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

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

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

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

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

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

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

Moreover, as said acrylic urethane-type resin, the acrylic urethane-type resin (U1) formed by polymerizing the urethane prepolymer (UP) and the vinyl compound containing a (meth)acrylic acid ester is preferable.

(Acrylic urethane resin (U1))

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As a method for introducing ethylenically unsaturated groups to both ends of the linear urethane prepolymer, the NCO group at the terminal of the linear urethane prepolymer formed by reacting a diol and a diisocyanate compound is reacted with a hydroxyalkyl (meth)acrylate can tell you how to do it.

As hydroxyalkyl (meth)acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2- Hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. are mentioned.

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

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

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

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

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

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

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

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

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

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

(olefin resin)

The olefin-based resin preferable 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, C2-C8 alpha-olefin is preferable, and, specifically, ethylene, propylene, butylene, isobutylene, 1-hexene, etc. are mentioned.

Among these, ethylene and propylene are preferred.

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

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

Examples of acid-modified olefin-based resins obtained by acid-modifying olefin-based resins include modified polymers obtained by graft polymerization of an unsaturated carboxylic acid or an anhydride thereof to the unmodified olefin-based resin described above. can

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

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

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

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

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

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

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

(Resin other than acrylic urethane resin and olefin resin)

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

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

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

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

(Non-solvent type resin composition (y1))

As the resin composition (y) used in one aspect of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer, and the above-described thermally expandable particles are blended. , a non-solvent type resin composition (y1) that does not contain a solvent.

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

The expandable substrate layer (Y1) satisfying the above requirement (1) is easily formed by irradiating energy rays to a coating film formed from the non-solvent type resin composition (y1).

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

The mass average molecular weight (Mw) of the oligomer contained in the non-solvent type resin composition (y1) is 50,000 or less, but is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, still more preferably 3,000 to 35,000, and even more Preferably it is 4,000 to 30,000.

Moreover, as said oligomer, among the resins contained in the resin composition (y) mentioned above, what is necessary is just to have a mass average molecular weight of 50,000 or less ethylenically unsaturated group, but the above-mentioned urethane prepolymer (UP) is preferable.

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

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

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

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

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

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

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

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

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

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

<Non-expandable base layer (Y2)>

Examples of the material for forming the non-expandable substrate layer (Y2) constituting the substrate (Y) include paper materials, resins, and metals. can be selected appropriately.

Here, in one aspect of the present invention, when the thermally expandable particles included in the expandable base layer (Y1) expand, irregularities are formed on the surface of the expandable base layer (Y1) on the non-expandable base layer (Y2) side. From the viewpoint of suppressing and preferentially forming irregularities on the surface of the pressure-sensitive adhesive layer (V1) side of the expandable base layer (Y1), the non-expandable base layer (Y2) is formed by the expansion of the thermally expandable particles. It is desirable to have rigidity to the extent that it is not deformed. Specifically, it is preferable that the storage elastic modulus (E') (t) of the non-expandable substrate layer (Y2) at the temperature (t) at the start of expansion of the thermally expandable particles is 1.1 × 10 ⁷ Pa or more.

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

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

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

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

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

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

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

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

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

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

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

However, it is preferable that the non-expandable substrate layer (Y2) does not contain thermally expandable particles. When the non-expandable substrate layer (Y2) contains thermally expandable particles, the smaller the content, the better. As the specific content of the thermally expandable particles, the total mass (100% by mass) of the non-expandable substrate layer (Y2) , it is usually less than 3% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass.

<Adhesive Layer (V)>

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

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

Hereinafter, each component contained in the adhesive composition (v) is described.

Also, when the support layer (II) includes the first pressure sensitive adhesive layer (V1-1) or (V1) and the second pressure sensitive adhesive layer (V1-2) or (V2), the first pressure sensitive adhesive layer (V1-1 ) or (V1), and the 2nd adhesive layer (V1-2) or (V2) can also be formed from the adhesive composition (v) containing each component shown below.

(adhesive resin)

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

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

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

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

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

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

Moreover, when using the support layer (II) which has a 1st adhesive layer (V1-1) or (V1) and a 2nd adhesive layer (V1-2) or (V2), it contacts curable resin layer (I), By containing an acrylic resin in the present first pressure sensitive adhesive layer (V1-1) or (V1), irregularities can be easily formed on the surface of the first pressure sensitive adhesive layer (V1-1) or (V1).

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

The content of the adhesive resin is preferably 35 to 100% by mass, based on the total amount (100% by mass) of the active ingredient of the PSA composition (v) or the total mass (100% by mass) of the PSA layer (V). It is preferably 50 to 100% by mass, more preferably 60 to 98% by mass, and still more preferably 70 to 95% by mass.

(crosslinking agent)

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

The crosslinking agent reacts with an adhesive resin having a functional group, and crosslinks the adhesive resins by using the functional group as a crosslinking origin.

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

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

Among these crosslinking agents, isocyanate-based crosslinking agents are preferable from the viewpoints of increasing cohesive force and improving adhesive force, and from viewpoints such as ease of availability.

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

(tackifier)

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

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

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

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

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

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

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

And when using 2 or more types of several tackifiers, it is preferable that the weighted average of the softening point of those several tackifiers belongs to the said range.

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

(Additive for adhesive)

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

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

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

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

In addition, when using the support layer (II) of the 3rd aspect which has the 2nd adhesive layer (V2) which is an expandable adhesive layer, as a formation material of the 2nd adhesive layer (V2) which is an expandable adhesive layer, In addition to the above-mentioned adhesive composition (v), it is formed as an expandable adhesive composition (v22) containing thermally expandable particles.

The thermally expandable particles are as described above.

The content of the heat-expandable particles is preferably 1 to 70% by mass, based on the total amount (100% by mass) of the active ingredients of the expandable PSA composition (v22) or the total mass (100% by mass) of the expandable PSA layer; More preferably, it is 2-60 mass %, More preferably, it is 3-50 mass %, Even 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, it is preferable that the pressure-sensitive adhesive composition (v) as a forming material of the non-expandable pressure-sensitive adhesive layer does not contain thermally expandable particles.

When containing thermally expansible particles, the content thereof is preferably as small as possible, relative to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (v) or the total mass (100% by mass) of the pressure-sensitive adhesive layer (V), It is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably less than 0.001% by mass.

In addition, as in the laminates 2a and 2b shown in Fig. 2, a support layer (II) having a first pressure-sensitive adhesive layer (V1-1) and a second pressure-sensitive adhesive layer (V1-2), which are non-expandable pressure-sensitive adhesive layers, is used. In this case, the storage shear modulus (G') (23) 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 is 5.0 × 10 ⁷ Pa or less, more preferably 1.0 × 10 ⁷ Pa or less.

When the storage shear modulus (G') 23 of the first pressure-sensitive adhesive layer (V1-1) that is a non-expandable pressure-sensitive adhesive layer is 1.0 × 10 ⁸ Pa or less, for example, the laminates 2a and 2b shown in FIG. 2 When it is configured as described above, the expansion of the thermally expansible particles in the expansible substrate layer (Y1) by thermal expansion treatment causes the surface of the first pressure-sensitive adhesive layer (V1-1) in contact with the cured resin layer (I') to It becomes easy to form irregularities.

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

The storage shear modulus (G′) (23) of the first PSA layer (V1-1), which is a non-expandable PSA layer at 23°C, is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 × 10 ⁴ Pa or more, more preferably 1.0 × 10 ⁵ Pa or more.

The light transmittance at a wavelength of 365 nm of the support layer (II) of the laminate of one aspect of the present invention is preferably 30% or more, more preferably 50% or more, still more preferably 70% or more. If the light transmittance is within the above range, when curable resin layer (I) is irradiated with energy rays (ultraviolet rays) through support layer (II), the degree of curing of curable resin layer (I) is further improved. Although the upper limit of the light transmittance of wavelength 365nm is not specifically limited, For example, it is possible to set it as 95% or less.

It is preferable that the base material (Y) and the pressure-sensitive adhesive layer (V) of the support layer (II) do not contain a colorant from the viewpoint of achieving the above light transmittance.

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

(object to be sealed)

Examples of objects to be sealed placed on a part of the surface of the curable resin layer (I) include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, substrates for panels, and the like. .

For example, when an object to be sealed is a semiconductor chip, the semiconductor chip with a cured resin layer can be manufactured by using the laminated body for curvature prevention of 1 aspect of this invention.

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

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

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

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

[Method of manufacturing laminate for preventing warping]

The laminated body for curvature prevention can be manufactured with the following method.

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

When the curable resin layer (I) is composed of two layers, each curable resin composition is formed on another peeling film, and both layers are overlapped so as to be in direct contact with each other to prepare a laminated curable resin layer. The first curable resin composition is coated and dried on a release film to form a first curable resin layer (X1-1), and then, on the first curable resin layer (X1-1), a second curable resin layer (X1 -2) or (X2) can be applied and dried to produce a layered curable resin layer.

By attaching the pressure-sensitive adhesive layer (V) of the support layer (II) to the curable resin layer (I) described above, or through a pressure-sensitive adhesive layer different from the support layer (II), the curable resin layer (I) and the support layer (II) By affixing, the laminated body for curvature prevention can be obtained.

For the support layer (II), a pressure-sensitive adhesive composition is coated and dried on a peeling film to form a pressure-sensitive adhesive layer (V), and then a resin material constituting the base material layer is applied to the pressure-sensitive adhesive layer and dried on the pressure-sensitive adhesive layer, or a sheet It can manufacture by attaching the upper base material to an adhesive layer, and forming a base material layer. When the base layer is composed of a plurality of layers, after forming the first base layer, the resin material constituting the second base layer is applied onto the first base layer and dried to form the second base layer. In the case of a support layer having a second pressure-sensitive adhesive layer on the second base layer, the second pressure-sensitive adhesive layer is formed by coating and drying the pressure-sensitive adhesive composition on the second base layer.

[First Method for Producing Cured Encapsulation]

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

Step (i): An object to be sealed is placed on a part of the first surface of the curable resin layer (I) in which the laminate for curvature prevention has.

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

Step (iii): While thermally curing the sealing material to form a cured sealing body containing the object to be sealed, the curable resin layer (I) is also thermally cured to form a cured resin layer (I′), Obtain a cured encapsulated body.

Process (iv): The cured resin layer (I') and the support layer (II) are separated at the interface by the treatment of expanding the thermally expandable particles, and a cured encapsulated body with a cured resin layer is obtained.

6 is a cross-sectional schematic diagram showing a step of manufacturing a cured encapsulated body with a cured resin layer, more specifically, a step of manufacturing a cured encapsulated body using the curvature-preventing laminate 1a shown in FIG. 1(b) It is a cross-sectional schematic diagram showing. Hereinafter, each process mentioned above is demonstrated, referring FIG. 6 suitably.

<Process (i)>

In step (i), an object to be sealed is placed on a part of the surface of the curable resin layer (I) of the laminate for curvature prevention of one aspect of the present invention.

In Fig. 6 (a), the state in which the adhesive surface of the adhesive layer (V1) of the support layer (II) is adhered to the support body 50 is shown using the laminated body 1b for curvature, and in Fig. 6 (b), A state in which the object to be sealed 60 is mounted on a part of the surface of the curable resin layer (I) is shown.

In addition, in FIG. 6, although the example using the laminated body 1b shown in FIG. 1(b) is shown, also in the case of using the laminated body for the curvature prevention of the other aspect of this invention, similarly, a support body, for curvature prevention The laminate and the object to be sealed are laminated or placed in this order.

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

It is preferable that the support body is affixed to the entire surface of the adhesive surface of the adhesive layer (V1) of the laminate.

Therefore, the support is preferably plate-shaped. Moreover, as shown in FIG. 6, it is preferable that the area of the adhesive surface of adhesive layer (V1) and the surface of the support body on the side to be stuck is more than the area of the adhesive surface of adhesive layer (V1).

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

As a material which comprises a specific support body, For example, metal materials, such as SUS; non-metallic inorganic materials such as glass and silicon wafer; resin materials such as epoxy resins, ABS resins, acrylic resins, engineering plastics, super engineering plastics, polyimide resins, and polyamideimide resins; Composite materials, such as a glass epoxy resin, etc. are mentioned, Among these, SUS, glass, a silicon wafer, etc. are preferable.

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

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

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

On the other hand, examples of objects to be sealed placed on a part of the surface of the curable resin layer (I) include semiconductor chips, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, substrates for panels, and the like. can In the following description, the case where a semiconductor chip is used as the object to be sealed 60 is described as an example.

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

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

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

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

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

The surface of the curable resin layer (I) of the present embodiment (in the example of FIG. 6 , the surface of the non-expandable thermosetting resin layer (X1) on the opposite side to the support layer (II)) has curability, but its adhesive strength is described above. By setting it as the description, at the time of bonding the semiconductor chip 60 as an object to be sealed with respect to the said surface of curable resin layer (I), the semiconductor chip 60 is fixed reliably, and it becomes easy to prevent position shift.

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

Therefore, the semiconductor chip is mounted on a part of the surface of the curable resin layer (I), and it is preferable to mount the plurality of semiconductor chips on the surface in a state in which a plurality of semiconductor chips are aligned at regular intervals. It is more preferable to arrange them on the surface in a state aligned in a matrix of multiple rows and multiple columns at regular intervals.

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

<Process (ii)>

In step (ii), the object to be sealed placed on the curable resin layer (I) and the first surface of the curable resin layer (I) at least in the periphery of the object to be sealed are covered with a thermosetting sealing material (hereinafter, " Also referred to as “covering treatment”).

In the coating treatment, first, the object to be sealed and at least the periphery 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 laminate 1b is attached on the support 50 and the semiconductor chip 60, which is an object to be sealed, is placed on the curable resin layer (I). The shaping die 70 is placed so as to be positioned within the mold of the mold 70. And into the molding space 72 formed between the molding die 70, the laminated body 1b, and the sealing object 60, the sealing material is injected through the injection hole 71.

The sealing material is also filled in gaps between a plurality of semiconductor chips while covering the entire exposed surface of the semiconductor chip 60, which is an object to be sealed.

When the molding die 70 is removed after the injection of the sealing resin and the resin molding are completed, as shown in FIG. 6(d), the surfaces of the semiconductor chip 60 and the curable resin layer (I) are both sealed 80).

In addition, when the encapsulant 80 is injected into the molding space 72 using a resin molding method of the type of injecting a resin material into a molding die, typified by the transfer molding method, along the surface of the curable resin (I) A flow of the encapsulant 80 occurs in the direction (see the arrow in FIG. 6(c)). In the production method of this aspect, the object to be sealed 60 is fixed by the curable resin layer (I), and the shear strength of the curable resin layer (I) to the adherend for measurement is set as the above-described object to be sealed. (60) It becomes easy to prevent shifting or tilting.

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

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

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

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

<Process (iii)>

In step (iii), the encapsulant after the coating treatment is thermally cured to form a cured encapsulant containing the object to be encapsulated. Moreover, the curable resin layer (I) is also cured to form a cured resin layer (I').

Specifically, as shown in FIG. 6(e), by curing the encapsulant 80, a cured encapsulant 85 covered with the semiconductor chip 60 as an object to be encapsulated is obtained by the cured encapsulant 81. . In this way, the semiconductor chip 60 is protected with a hard material while maintaining its layout. At this time, in the production method of this aspect, since the thermosetting resin layer (X1) is used as the curable resin layer (I), the curing start temperature thereof is set to the same level as the curing start temperature of the thermosetting encapsulant 80. By doing this, or when both curing start temperatures are different, by heating to a higher curing start temperature or higher, curing of the encapsulant and curing of the thermosetting resin layer with one heating (creation of the cured thermosetting resin layer (X1 ') ) can be 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 this aspect, by forming the curable resin layer (I), the difference in shrinkage stress between the two surfaces of the obtained cured sealed body 85 can be reduced, and the cured sealed body 85 can effectively suppress the warpage that occurs in In particular, by thermally curing the thermosetting resin layer (X1) at the same time as the thermal curing of the encapsulant, the difference in shrinkage stress between the two surfaces of the cured encapsulant 85 can be reduced even in the curing process, so that the warpage is more effective. are suppressed

As described above, the heating temperature for curing in step (iii) is lower than the heating temperature for expansion in step (iv).

<Process (iv)>

In step (iv), the cured resin layer (I') and the support layer (II) are separated at the interface by performing a treatment to expand the thermally expandable particles included in the expandable substrate layer (Y1), and the cured resin layer An adhesive curing encapsulated body is obtained.

6(f) shows that the expandable substrate layer (Y1) becomes an expanded expandable substrate layer (Y1') by the treatment of expanding the thermally expandable particles, and the cured resin layer (I') and the expanded support layer (II') are formed. ) shows the separated state at the interface of

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

In addition, the presence of the cured resin layer (I') has a function of effectively suppressing warpage occurring in the cured encapsulation body, and contributes to improvement in reliability of the object to be encapsulated.

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

The “temperature above the expansion start temperature (t)” at which the thermally expandable particles expand is preferably “expansion start temperature (t) + 10 ° C.” or more and “expansion start temperature (t) + 60 ° C.” or less, and “expansion start temperature (t) + 15 ° C.” or more and “expansion start temperature (t) + 40 ° C.” or less is more preferable.

In addition, the heating method for expanding the heat-expandable particles is not particularly limited, and examples thereof include a heating method using a hot plate, oven, firing furnace, infrared lamp, hot air blower, etc. From the viewpoint of facilitating separation of the stratum (I') at the interface (P), a method in which a heat source during heating can be provided on the side of the support (50) is preferable.

The cured encapsulated body 200 with a cured resin layer obtained in this way is further subjected to necessary processing thereafter. The cured resin layer as a warpage correction layer is removed by grinding or the like while the semiconductor device is finally manufactured, and does not remain in the semiconductor device as the final product.

[Second Manufacturing Method of Cured Encapsulation]

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

Step (i'): An object to be sealed is placed on a part of the surface on the opposite side to the first layer of the energy ray-curable resin layer (X2), which is the first surface of the curable resin layer of the laminate for warpage prevention.

Step (ii')-1: Energy ray curable resin layer (X2) is cured by irradiation with energy rays.

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

Step (iii'): While thermally curing the sealing material to form a cured sealing body containing the object to be sealed, the curable resin layer (I) is also thermally cured to form a cured resin layer (I'), Obtain a cured encapsulated body.

Process (iv): The cured resin layer (I') and the support layer (II) are separated at the interface by the treatment of expanding the expandable particles, and a cured sealed body with a cured resin layer is obtained.

Hereinafter, each process will be described in detail, but in order to avoid being redundant, it is assumed that the same steps and operations as those in the first aspect of the production method described above are applied as they are, in order to avoid being redundant. omit the explanation.

<Process (i')>

In step (i'), an object to be sealed is placed on a part of the surface of the curable resin layer (I) of the laminate for curvature prevention of one aspect of the present invention.

In Fig. 7 (a), the curable resin layer (I) is formed of a thermosetting resin layer (X1-1) on the side of the support layer (II) and an energy ray-curable resin layer (X2) on the side opposite to the support layer (II). The state in which the adhesive surface of the adhesive layer (V1) of the support layer (II) was adhered to the support body 50 using the laminated body 5 for prevention (see FIG. 5) is shown, and in FIG. 7(b), the curable resin layer (I) shows a state in which the object to be sealed 60 is placed on a part of the surface.

The surface of the curable resin layer (I) of the present embodiment (in the example of FIG. 7 , the surface of the energy ray-curable resin layer (X2) on the opposite side to the support layer (II)) has curability, but its adhesive strength is A value obtained by attaching the first surface to a glass plate at a temperature of 70°C, peeling the curable resin layer (I) at a temperature of 23°C, a peeling angle of 180°, and a peeling rate of 300 mm/min, and measuring 1.7 N/ By setting it as 25 mm or more, at the time of bonding of the object to be sealed 60 with respect to the said surface of the curable resin layer (I), the object to be sealed 60 is reliably fixed, and it becomes easy to prevent positional displacement including a tilt shift .

<Process (ii')-1>

Step (ii')-1 is a step of irradiating the energy ray-curable resin layer (X2) with an energy ray to form a cured resin layer (I*) obtained by curing the energy ray-curable resin layer (X2).

7(c) shows a partially cured (in other words, the layer on the first surface side) by curing the energy ray-curable resin layer (X2) in this step to form a cured energy ray-curable resin layer (X2'). A state in which this cured) cured resin layer (I*) is formed is shown.

The type and irradiation conditions of the energy ray are not particularly limited as long as the type and condition are cured to the extent that the energy ray-curable resin layer (X2) sufficiently exhibits its function, and may be appropriately selected from among known methods depending on the desired process.

When an ultraviolet curable resin composition is used as a material constituting the energy ray curable resin layer (X2), the material selection range is wide, and as an energy ray source for curing the composition, an ultraviolet irradiation device that is easy to obtain and has excellent handling properties can be used.

The intensity 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 3 to 1,000 mJ/cm 2 . it is desirable

Prior to the step (iii') including thermal curing, by irradiating energy rays in step (ii')-1, it is avoided that the curing reaction progresses due to cleavage of the energy beam curable resin by heating, and the energy rays curing reaction can proceed efficiently. In addition, it is also possible to prevent contamination of the object to be sealed by volatilization of low-molecular components (such as a photopolymerization initiator) contained in the energy ray-curable resin by heating. In addition, by curing the energy ray-curable resin layer with energy rays prior to thermal curing, curing shrinkage of the energy ray-curable resin (X2) by heating for thermal curing is prevented, and the encapsulating resin and the energy ray-curable resin (X2 ) can be prevented from deteriorating the adhesion between them.

<Process (ii')-2>

After the object to be sealed 60 is disposed and the cured energy ray-curable resin layer (X2') is formed by irradiating energy rays, in step (ii')-2, in the same manner as described in Fig. 6(d) , Inject the encapsulant 80 using a molding die (not shown). At this time, although the flow of the sealing material occurs in the surface direction, the object to be sealed 60 is fixed by the cured energy ray-curable resin layer (X2'), and the curable resin layer (I) is fixed to the adherend for measurement. For the shear strength, a silicon chip having a thickness of 350 μm with a mirror surface of 3 mm × 3 mm was used as the above-mentioned adherend for measurement, and the mirror surface of the adherend for measurement at a temperature of 70 ° C. for 1 second at 130 gf was applied to a curable resin layer ( It is easy to prevent the object to be sealed 60 from shifting or tilting by setting it to 20 N/(3 mm × 3 mm) or more as a value when applied by applying pressure to I) and measured at a speed of 200 µm/s lose

When the injection of the sealing resin is completed, as shown in FIG. 7(d), the surface of the object to be sealed 60 and the cured energy ray-curable resin layer (X2') around it is covered with the sealing material 80. all.

<Process (iii')>

In step (iii'), the encapsulant after the coating treatment is thermally cured to form a cured encapsulant containing the object to be encapsulated. Further, the thermosetting resin layer (X1-1) is also cured to form a cured resin layer (X1-1'), and a cured resin layer (I') in which both the first and second layers are cured is formed.

By curing the sealing material 80, as shown in FIG. 7(e), the cured sealing material 81 covers the object to be sealed 60 and becomes a cured sealing body 85. At this time, in this production example, since the thermosetting resin layer (X1-1) is used as the curable resin layer (I), by setting the thermosetting encapsulant 80 and the curing start temperature to the same level, or curing When the initiation temperatures are different, by heating to a higher curing initiation temperature or higher, curing of the encapsulant and curing of the thermosetting resin layer can be simultaneously performed with one heating.

<Process (iv)>

In step (iv), by performing a treatment to expand the expandable particles included in the expandable substrate layer (Y1), the cured resin layer (I') and the support layer (II) are separated at the interface, and the cured resin layer is attached. Obtain a cured encapsulated body.

7(f) shows that the expandable base layer (Y1) becomes the expandable base layer (Y1') by the treatment of expanding the expandable particles, and the interface between the cured resin layer (I') and the expanded support layer (II') is shown. indicates a state of separation.

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

After the cured encapsulated body 85 is manufactured in the above procedure, necessary processing is given to the cured encapsulated body 201 with a cured resin layer.

Example

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

In the following description, curable resin layer (I) shall mean both "energy ray-curable resin layer (X2)" and "thermosetting resin layer (X1-1), (X1-2)" .

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

<Mass average molecular weight (Mw)>

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

(Measuring conditions)

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

Column temperature: 40 ℃

Developing solvent: tetrahydrofuran

·Flow rate: 1.0 ml/min

<Measurement of thickness of each layer>

It was measured using a static pressure thickness meter manufactured by Techlock Co., Ltd. (model number: "PG-02J", standard specifications: based on JIS K6783, Z1702, Z1709).

<Minimum Curing Temperature of Curable Resin Layer>

A plurality of samples for measurement are prepared in advance using the same composition, and each is attributed to the curing reaction at set temperatures at intervals of 60°C to 20°C using a differential scanning thermal spectrometer (Q2000, manufactured by TA Instruments). The time until the peak disappears was measured. At this time, the temperature was raised from room temperature to the set temperature at a temperature increase rate of 10°C/min. In the above measurement, the temperature at which the curing reaction peak disappeared in 2 hours was determined as the lowest curing temperature.

<Separability after curing of curable resin layer>

Prepare two samples in which a curable resin layer is attached to a glass plate with a support layer (float plate glass 3 mm (JIS R3202 product) manufactured by Yuko Corporation), one is heated at 130 ° C. for 2 hours, and the other is 160 ° C. heated for 1 hour. The sample for measurement after heating was heated for 3 minutes at the maximum expansion temperature + 30°C described later of the supporting layer of each sample with a hot plate. After standing to cool until it reached normal temperature, the peelability of the support layer and the cured resin layer was evaluated. When the curable resin layer did not self-peel (separate without external force), the edge of the curable resin layer was pinched with tweezers, and peeled at the interface between the support layer and the curable resin layer, and evaluated.

○ = The entire surface self-peeled, and no abnormality was observed in the external appearance of the peeled surface of the cured resin layer.

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

x = The point where peeling could not be carried out even with tweezers, or could not be peeled occurred over the whole surface of the curable resin layer.

<Measurement of Expansion Start Temperature (t) and Maximum Expansion Temperature of Thermally Expandable Particles>

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

A sample was prepared by adding 0.5 mg of thermally expandable particles to be measured to an aluminum cup having a diameter of 6.0 mm (internal diameter of 5.65 mm) and a depth of 4.8 mm, and an aluminum lid (diameter of 5.6 mm and thickness of 0.1 mm) was placed thereon. .

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

Further, the maximum expansion temperature refers to a temperature at which the amount of displacement is maximized.

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

The amount of displacement obtained at the time of measuring the maximum expansion temperature described above is taken as the thickness (Dm) of the support layer at the maximum expansion temperature. In addition, the thickness (Da) of the support layer when each support layer is heated under the curing condition 1 of the curable resin layer (heating at 130 ° C. for 2 hours) and the curing condition 2 of the curable resin layer (heating at 160 ° C. for 1 hour) The thickness (Db) of the support layer when heated was measured. Then, the values of (Da/Dm) x 100 and (Db/Dm) x 100 were obtained, and the expansion coefficient of the support layer at the curing temperature of the curable resin layer was determined.

<Measurement of adhesive force of thermosetting resin layer>

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

And the peeling film was removed and the surface of the exposed thermosetting resin layer was affixed to the smooth surface of the glass plate (3 mm float plate glass by Yuko Corporation (JIS R3202 product)) which is an adherend. The sticking temperature of the thermosetting resin layer (X1) was 70°C. Then, the glass plate to which each layer was attached was allowed to stand for 24 hours in an environment of 23 ° C. and 50% RH (relative humidity), and then, in the same environment, based on JIS Z0237: 2000, by the 180 ° peeling method, The adhesive strength at 23°C was measured at a tensile speed of 300 mm/min.

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

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

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

<Evaluation of warpage>

On a 12-inch, 100 μm-thick silicon wafer, the thermosetting resin layer of the warp-preventing laminate of Examples 1 and 2 was respectively affixed, and an epoxy resin composition was applied to the surface opposite to that to which the thermosetting resin layer was affixed at a thickness of 30 μm. applied. And the layer of the said epoxy resin composition and the thermosetting resin layer of each laminate were heated and hardened. After completion of curing, the silicon wafer with the cured resin layer was placed on a level table, and then visually observed, and the presence or absence of warpage was evaluated based on the following criteria.

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

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

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

As the epoxy resin composition, a mixture of "Ephofix Resin" manufactured by Struers and a curing agent "Ephofix Hardener" manufactured by the company was used. In this evaluation, in order to simplify the experimental procedure, a large-diameter silicon wafer is used as an adherend, while an epoxy resin layer is formed on the back side of the adherend to provide a condition in which warpage easily occurs, so that warpage can be evaluated. made it appropriate.

Preparation Example 1

(1) Preparation of Curable Resin Composition

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

・Acrylic polymer: blending amount = 21 parts by mass

An acrylic polymer formed 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 (mass average molecular weight: 800,000, Glass transition temperature: -28°C), equivalent to the above component (A1).

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

Liquid bisphenol A type epoxy resin (made by Nippon Catalyst, product name "BPA328", epoxy equivalent = 220-240 g/eq), equivalent to the above component (B1).

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

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

Epoxy compound (3): blending 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), equivalent to the above component (B1).

Heat curing agent: blending amount = 0.5 parts by mass

Dicyandiamide (manufactured by ADEKA, product name "Adeka Hardner EH-3636AS", amount of active hydrogen = 21 g/eq), equivalent to the above component (B2).

・Curing accelerator: blending amount = 0.5 parts by mass

2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Industrial Co., Ltd., product name "Cuazole 2PHZ"), equivalent to the above component (B3).

Silane coupling agent: blending amount = 0.4 parts by mass

Epoxy group-containing oligomeric silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"), equivalent to the above component (D).

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

Spherical silica filler (made by Adomatex, product name "SC2050MA", average particle diameter = 0.5 µm), equivalent to the above component (E).

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

Spherical silica filler (manufactured by Tatsumori, product name "SV-10", average particle diameter = 8 µm), equivalent to the above component (E).

(2) formation of thermosetting resin layer

The solution of the thermosetting resin composition prepared in (1) above is applied to the peeling treated surface of the easy release film to form a coating film, and the coating film is dried at 120 ° C. for 2 minutes to form a thermosetting resin layer having a thickness of 25 μm. did Let this be curable resin layer 1.

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

Preparation Example 2

(1) Manufacture of support layer

A heat-peelable laminate (manufactured by Nitto Denko, product name "Riva Alpha (NITTO 3195)") having a structure in which a heat-peelable adhesive layer was formed on a polyester film base material was used as a support layer. Let this be the support layer 1. In addition, when manufacturing the laminated body for bending prevention mentioned later, the peeling liner formed on the surface of the heat-peelable adhesive layer was peeled off and used. The support layer 1 has a base material and an adhesive layer containing thermally expandable particles, and when heated to an expansion start temperature of 170°C or higher, the thermally expandable particles expand to generate fine concavo-convex shapes on the surface of the adhesive layer.

Preparation Example 3

(1) Synthesis of urethane prepolymer

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

Then, a solution obtained by diluting 1.44 parts by mass (solid content) of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by mass of toluene was added, and further at 80°C until the isocyanate groups at both ends disappeared. It was made to react for 6 hours, and the urethane prepolymer with a mass average molecular weight of 2.9 million was obtained.

(2) Synthesis of acrylic urethane resin

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

Then, in the reaction vessel, a solution in which 2.2 parts by mass (solid content) of a radical initiator (manufactured by Nippon Finechem Co., Ltd., product name "ABN-E") was further diluted with 210 parts by mass of toluene was maintained at 105°C for 4 hours. Dropped across.

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

(3) Preparation of pressure-sensitive adhesive composition (1)

To 100 parts by mass of the solid content of the acrylic copolymer (i) below, which is an adhesive resin, 5.0 parts by mass (solid content) of the following isocyanate-based crosslinking agent (i) was blended, diluted with toluene, stirred uniformly, and the solid content concentration (effective Component concentration) A 25% by mass adhesive composition (1) was prepared.

-Acrylic copolymer (i): mass average molecular weight having structural units derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) 600,000 acrylic copolymer.

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

(4) Preparation of pressure-sensitive adhesive composition (2)

To 100 parts by mass of the solid content of the acrylic copolymer (i) below, which is an adhesive resin, 5.0 parts by mass (solid content) of the following isocyanate-based crosslinking agent (i) was blended, diluted with toluene, stirred uniformly, and the solid content concentration (effective Component concentration) A 25% by mass adhesive composition (2) was prepared.

-Acrylic copolymer (i): mass average molecular weight having structural units derived from a raw material monomer consisting of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) 600,000 acrylic copolymer.

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

(5) Formation of pressure-sensitive adhesive layer (1)

On the surface of the release agent layer of the easy release film, the adhesive composition (1) prepared in Production Example 3(1) was applied to form a coating film, and the coating film was dried at 100 ° C. for 60 seconds to obtain a pressure-sensitive adhesive layer having a thickness of 5 μm ( 1) was formed.

(6) Formation of pressure-sensitive adhesive layer (2)

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

(7) Manufacture 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 "Cosmo Shine A4100") having a thickness of 50 µm as a base material.

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

To 100 parts by mass of the solid content of the acrylic urethane resin obtained in Production Example 3 (2), 6.3 parts by mass (solid content) of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, product name "Colonate L", solid content concentration: 75 mass%), a catalyst 1.4 parts by mass (solid content) of dioctyltinbis(2-ethylhexanoate), and the thermally expandable particles (manufactured by Kureha Co., Ltd., product name "S2640", expansion onset temperature (t) = 208 ° C., average particle diameter ( D ₅₀ ) = 24 μm, 90% particle size (D ₉₀ ) = 49 μm) were blended, diluted with toluene, and stirred uniformly to prepare a resin composition having a solid content concentration (active ingredient concentration) of 30% by mass. The content of the thermally expandable particles was 20% by mass with respect to the total amount (100% by mass) of active ingredients in the obtained resin composition.

The resin composition containing the thermally expandable particles was applied onto the anchor layer described above to form a coating film, and the coating film was dried by heating at 100°C for 2 minutes to form a thermally expandable layer having a thickness of 35 µm.

On this thermally expandable layer, the said adhesive layer (1) was stuck. In this way, a support layer in which release films were laminated on the front and back was prepared. Let this be the support layer 2.

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

Production Example 4

The thermally expandable particles are changed to thermally expandable microcapsules manufactured by Nippon Fillite Co., Ltd. (product name “Expancel 031-40DU”, expansion start temperature (t) = 80° C.), and the drying conditions after applying the resin composition to form a coating film are: A support layer was manufactured in the same procedure as in Production Example 3, except that the ambient temperature was changed to 100°C for 1 minute. Let this be the support layer 3.

The support layer 3 has a pressure-sensitive adhesive layer and a base material containing thermally expandable particles, and when heated to 80°C or higher, the thermally expandable particles expand to form fine concavo-convex shapes on the surface of the support layer.

Preparation Example 5

Thermally expandable particles were changed to Nippon Fillite Co., Ltd. thermally expandable microcapsules (product name “Expancel 053-40DU”, expansion start temperature (t) = 100° C.), and drying conditions after applying a resin composition to form a coating film were set to atmosphere A support layer was prepared in the same manner as in Production Example 3, except that the temperature was changed to 100°C for 1 minute. Let this be the support layer 4.

The support layer 4 has a pressure-sensitive adhesive layer and a base material containing thermally expandable particles, and when heated to 100°C or higher, the thermally expandable particles expand to form fine concavo-convex shapes on the surface of the support layer.

In Production Examples 4 and 5, when producing the support layer, the drying temperature after coating the resin composition to form the coating film is set higher than the expansion initiation temperature (t) of the thermally expandable particles. Because of the temperature, no foaming was observed in the formed supporting layer.

Preparation Example 6

As the thermally expandable particles, using thermally expandable microcapsules manufactured by Nippon Fillite Co., Ltd. (product name "Expancel 920-40DU", expansion start temperature (t) = 120°C), the drying conditions after coating the resin composition to form a coating film, A support layer was manufactured in the same procedure as in Production Example 3, except that the ambient temperature was changed to 100°C for 1 minute. Let this be the support layer 5.

The support layer 5 has a pressure-sensitive adhesive layer and a base material containing thermally expandable particles, and when heated to 120°C or higher, the thermally expandable particles expand to form fine concavo-convex shapes on the surface of the support layer.

(Example 1)

Remove the peeling film laminated on the pressure-sensitive adhesive layer 2 of the support layer 2 prepared in Production Example 3, and the adhesive surface of the exposed pressure-sensitive adhesive layer 2 and the surface of the curable resin layer 1 formed in Production Example 1 Lamination for curvature prevention with release film in which heavy release film/adhesive layer (1)/base material/anchor layer/thermal expansible layer/adhesive layer (2)/thermosetting resin layer/release film are laminated in this order by bonding together got a sieve

(Example 2)

The peeling film laminated on the pressure-sensitive adhesive layer of the support layer 1 of Production Example 2 is removed, and the adhesive surface of the exposed pressure-sensitive adhesive layer 2 and the surface of the curable resin layer 1 formed in Production Example 1 are bonded together, An adhesive layer/thermosetting resin layer/release film were laminated in this order to obtain a laminate for curvature prevention with a release film.

(Comparative Example 1)

Remove the peeling film laminated on the second pressure-sensitive adhesive layer of the support layer 3 prepared in Production Example 4, and attach the surface of the exposed pressure-sensitive adhesive layer 2 to the surface of the curable resin layer 1 formed in Production Example 1. Combined, heavy release film / pressure-sensitive adhesive layer (1) / base material / anchor layer / thermally expandable layer / pressure-sensitive adhesive layer (2) / thermosetting resin layer / release film were laminated in this order to obtain a laminate for warping prevention with release film.

(Comparative Example 2)

Remove the peeling film laminated on the second pressure-sensitive adhesive layer of the support layer 4 prepared in Production Example 5, and attach the surface of the exposed pressure-sensitive adhesive layer 2 and the surface of the curable resin layer 1 formed in Production Example 1. Combined, heavy release film / pressure-sensitive adhesive layer (1) / base material / anchor layer / thermally expandable layer / pressure-sensitive adhesive layer (2) / thermosetting resin layer / release film were laminated in this order to obtain a laminate for warping prevention with release film.

(Comparative Example 3)

Remove the peeling film laminated on the pressure-sensitive adhesive layer 2 of the support layer 5 prepared in Production Example 6, and the adhesive surface of the exposed pressure-sensitive adhesive layer 2 and the surface of the curable resin layer 1 formed in Production Example 1 By bonding, heavy release film / pressure-sensitive adhesive layer (1) / base material / anchor layer / thermal expansion layer / pressure-sensitive adhesive layer (2) / thermosetting resin layer / release film were laminated in this order to obtain an anti-warping laminate with release film.

The laminates for curvature prevention obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were measured and evaluated according to the above-described measuring method and evaluation procedure. A result is shown in Table 1.

As is clear from the results of Table 1, in Examples 1 and 2, when the curable resin layer was cured at 130 ° C. for 2 hours, the cured resin layer and the support layer had good peelability, and the occurrence of warpage was sufficiently suppressed. . In Examples 1 and 2, even 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 did not interfere in practical use, and the occurrence of warpage was sufficiently suppressed. In particular, in Example 2, curing at 160 ° C. caused the support layer to foam to some extent, and the release property of the support layer also slightly decreased. It is equivalent to the case of and was able to obtain a cured encapsulated body in a shorter time.

On the other hand, in Comparative Examples 1 to 3, the peelability of the curable resin layer and the support layer was greatly reduced, and it was not possible to peel at the interface between the support layer and the cured resin layer.

(I): curable resin layer
(I'): cured resin layer
(I*): Partially cured curable resin layer
(II): support layer
(II'): expanded support layer
(V): pressure-sensitive adhesive layer
(V1): (1st) pressure-sensitive adhesive layer
(V1-1): 1st adhesive layer
(V2), (V1-2): 2nd adhesive layer
(X1), (X1-1), (X1-2): thermosetting resin layer
(X1'): Cured thermosetting resin layer
(X1-1'): Cured thermosetting resin layer
(X2): energy ray curable resin layer
(X2'): Cured energy ray curable resin layer
(Y): description
(Y1): Intumescent substrate layer
(Y1'): expanded intumescent substrate layer
(Y2): non-expandable substrate layer
1a, 1b, 2a, 2b, 3, 4, 5: laminate for bending prevention
50: support
60: object to be encapsulated (semiconductor chip)
70: forming type
71: injection hole
72: molding space
80: encapsulant
81: cured encapsulant
85: curing encapsulation body
200: cured encapsulation body with cured resin layer
P: interface

Claims (10)

It has a curable resin layer (I) containing a thermosetting resin layer (X1) and a support layer (II) 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), and at least one of the base material (Y) and the pressure-sensitive adhesive layer (V) contains thermally expandable particles,
While the curable resin layer (I), the pressure-sensitive adhesive layer (V), and the base material (Y) are arranged in this order, the adhesive surface of the curable resin layer (I) is arranged on the opposite side to the pressure-sensitive adhesive layer (V),
The minimum curing temperature (T 1 ) at which curing of the curable resin layer (I) is completed within 2 hours to become the cured resin layer (I _′ ) is lower than the foaming start temperature (T ₂ ) of the thermally expandable particles,
Curable resin layer (I) wherein the difference (T ₂ - T ₁ ) between the minimum curing temperature (T ₁ ) of the curable resin layer (I) and the foaming start temperature (T ₂ ) of the thermally expandable particles is 20°C to 100°C ) A laminate for curing prevention of a cured encapsulated body produced by encapsulating an object to be sealed on the adhesive surface of the above. According to claim 1,
An anti-warping laminate, wherein the difference (T ₂ - T ₁ ) between the minimum curing temperature (T ₁ ) of the curable resin layer (I) and the foaming start temperature (T ₂ ) of the thermally expandable particles is 40°C to 100°C. According to claim 1,
The curable resin layer (I) has two or more layers of the thermosetting resin layer (X1), and the minimum value (T _1a ) of the minimum curing temperature (T ₁ ) in the two or more layers of the thermosetting resin layer (X1) is the thermal expansion A layered product for curvature prevention that is lower than the foaming start temperature (T ₂ ) of the sexual particles. According to claim 1,
The laminated body for curvature prevention whose thickness of the thermosetting resin layer (X1) is 1-500 micrometers. According to claim 1,
The laminate for curvature prevention in which the base material (Y) has an expandable base material layer (Y1) containing the above thermally expandable particles. According to claim 5,
The laminated body for curvature prevention whose adhesive layer (V) is a non-expandable adhesive layer. According to claim 5,
The base material (Y) has a non-expandable base layer (Y2) and an expandable base layer (Y1),
The laminate for curvature prevention in which the support layer (II) has a non-expandable substrate layer (Y2), an expandable substrate layer (Y1), and an adhesive layer (V) in this order. According to any one of claims 1 to 7,
The curable resin layer (I) has a first layer disposed on the support layer (II) side and a second layer disposed on the adhesion surface side,
The first layer is a thermosetting resin layer (X1-1),
The second layer is an energy ray-curable resin layer (X2). A method for producing a curing encapsulated body using the curvature-preventing laminate according to any one of claims 1 to 7,
A step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) of the above-mentioned laminate for curvature;
A step of covering the object to be sealed and the adhesive surface of the curable resin layer (I) of at least the periphery of the object to be sealed with a thermosetting sealing material;
The encapsulant is thermally cured to form a cured encapsulated body containing the object to be encapsulated, and the curable resin layer (I) is also thermally cured to form a cured resin layer to obtain a cured encapsulated body with a cured resin layer. A method for producing a curing encapsulated body comprising a step. A method for producing a curing encapsulated body using the warp-preventing laminate according to claim 8,
A step of placing an object to be sealed on a part of the adhesive surface of the curable resin layer (I) of the layered body for curvature prevention;
a step of curing the energy ray-curable resin layer (X2) by irradiating energy rays;
A step of covering the object to be sealed and the adhesive surface of the curable resin layer (I) of at least the periphery of the object to be sealed with a thermosetting sealing material;
The encapsulant is thermally cured to form a cured encapsulant containing the object to be encapsulated, and the curable resin layer (I) is also thermally cured to form a cured resin layer (I′), thereby curing with the cured resin layer. A method for producing a cured encapsulated body, including a step of obtaining an encapsulated body.

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