TWI801426B - Anti-warping laminate of hardened sealing body, and manufacturing method of hardened sealing body - Google Patents

Abstract

A warp-resistant laminate for a cured sealing body, comprising a curable resin layer (I) comprising a thermosetting resin layer (X1), and a support layer (II) supporting the curable resin layer (I); The resin layer (I) has an adhesive surface, 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 adhesive layer (V) One is to include heat-expandable particles, curable resin layer (I), and adhesive layer (V), and substrate (Y), while being arranged in this order, the aforementioned adhesive surface of curable resin layer (I) The lowest curing temperature (T ₁ ) at which the curing of the curable resin layer (I) is completed within 2 hours to form the cured resin layer (I') in order to be placed on the opposite side of the adhesive layer (V) is, compared to the aforementioned thermal expansion The foaming initiation temperature (T ₂ ) of the active particles is lower, and it is obtained by sealing the object to be sealed in the aforementioned adhesive surface of the curable resin layer (I).

Description

Anti-warping laminate of hardened sealing body, and manufacturing method of hardened sealing body

The present invention relates to a warpage-resistant laminate related to a hardened sealing body, and a method for manufacturing the hardened sealing body.

In recent years, along with the miniaturization, light weight and high performance of electronic equipment, semiconductor chips are usually packaged in a way approaching their size. These packages are also called CSP (Chip Scale Package). Examples of CSP include WLP (Wafer Level Package), which is completed from wafer-size processing to the final step of packaging, and PLP (Panel Level Package) etc.

WLP and PLP can be divided into fan-in (Fan-In) type and fan-out (Fan-Out) type. In the fan-out (Fan-Out) type WLP (hereinafter, also referred to as "FOWLP") and PLP (hereinafter, also referred to as "FOPLP") processes, the semiconductor wafer is sealed in a larger area than the wafer size. coating to form a hardened sealing body of the semiconductor wafer, and the wire redistribution layer (RDL) and external electrodes are not only formed on the circuit surface of the semiconductor wafer, but also formed in the surface area of the sealing material.

For example, FOWLP and FOPLP can be hardened and sealed by placing a plurality of semiconductor wafers on a temporary fixing sheet, coating with a thermosetting sealing material, and thermosetting the sealing material. The hardening step of the body, the separation step of separating the hardened sealing body from the temporary fixing sheet, and the step of forming a wire redistribution layer (RDL) on the surface of the exposed semiconductor wafer side (hereinafter, the processing of the coating step and the hardening step is also referred to as "sealing processing").

Patent Document 1 discloses a heat-peelable adhesive sheet for temporary fixing of electronic components, in which a thermally expandable adhesive layer containing thermally expandable microspheres is provided on at least one side of a substrate. In the production of FOWLP and FOPLP, it is presumed that the heat-peelable adhesive sheet described in Patent Document 1 can also be used. [Prior Art Literature] [Patent Document]

[Patent Document 1] JP-A-2001-131507

[Problem to be solved by the invention]

However, as a result of research by the present inventors, it has been found that the adhesive sheet described in Patent Document 1 is used as a temporary fixing sheet, and when a hardened sealing body is produced, when the above-mentioned temporary fixing layer is heated to foam the thermally expandable particles, The hardened resin layer formed by the first stage of heating before heating and foaming may cause the possibility that the temporary hardened layer cannot be peeled off. This problem tends to become more prominent as the package size of FOWLP, FOPLP, etc. increases. A cured seal with poor peeling may not only damage the object to be sealed, such as a semiconductor chip, but may also cause, for example, a part of the thermally expandable adhesive layer to remain on the cured resin layer, or the body of the cured resin layer to be damaged. The steps such as grinding or cutting of the hardened sealing body carried out in the subsequent steps cannot be carried out correctly and other disadvantages.

The present invention, in view of the above problems, proposes a support layer and a curable resin layer, and at the same time that the object to be sealed is fixed on the surface of the curable resin layer to perform sealing processing, it can be provided as a product formed by the sealing process. Cured resin layer of the anti-warping layer of the hardened sealing body, anti-warp laminate capable of preventing peeling failure between the curable resin layer and the support layer, and production of a cured sealed body using the anti-warp laminate method for purpose. [How to solve the problem]

The present inventors, as a result of intensive research on solving the above-mentioned problems, found that the above-mentioned problems can be solved by setting the adhesive force of the curable resin layer within a specific range, and thus completed the present invention. That is, the present invention provides the following [1] to [10].

[1] A warpage-resistant laminate of a cured sealing body comprising a curable resin layer (I) including a thermosetting resin layer (X1), and a support layer (II) supporting the curable resin layer (I). ); it is characterized in that the curable resin layer (I) has an adhesive surface, the support layer (II) has a base material (Y) and an adhesive layer (V), the base material (Y) and an adhesive layer At least one of the agent layers (V) comprises heat-expandable particles, the curable resin layer (I), the adhesive layer (V), and the substrate (Y), while the curable resin layer is arranged in this order. The aforementioned adhesive surface of (I) is configured on the opposite side to the adhesive layer (V), and the hardening of the curable resin layer (I) is completed within 2 hours to form the minimum hardening temperature (T ₁ ) is lower than the foaming initiation temperature (T ₂ ) of the aforementioned heat-expandable particles, and is obtained by sealing the object to be sealed in the aforementioned adhesive surface of the curable resin layer (I). [2] The warpage-resistant laminate as described in [1] above, wherein the difference between the minimum curing temperature (T ₁ ) of the curable resin layer (I) and the foaming initiation temperature (T ₂ ) of the thermally expandable particles is (T ₂ -T ₁ ) is 20°C to 100°C. [3] The anti-warping laminate according to [1] or [2] above, wherein the curable resin layer (I) has two or more thermosetting resin layers (X1), and the two or more layers The minimum value (T _1a ) of the lowest curing temperature (T ₁ ) in the thermosetting resin layer (X1) is lower than the above-mentioned foaming start temperature (T ₂ ) of the thermally expandable particles. [4] The laminate according to any one of the above [1] to [3], wherein the thickness of the thermosetting resin layer (X1) is 1 to 500 μm. [5] The laminate according to any one of the above [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 adhesive layer (V) is a non-expandable adhesive layer. [7] The laminate according to the above [5] or [6], wherein the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1), and the support layer (II) In order to have a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (V). [8] The laminate according to any one of the above [1] to [7], wherein the curable resin layer (I) has a first layer disposed on the support layer (II) side, and is disposed on the side of the support layer (II). For the second layer on the adhesive surface side, the first layer is a thermosetting resin layer (X1-1), and the second layer is an energy ray-curing resin layer (X2). [9] A method for producing a cured sealing body, which is a method of manufacturing a cured sealing body using the warpage-resistant laminate described in any one of the above [1] to [7], characterized by comprising: The step of placing the object to be sealed by using a part of the adhesive surface of the curable resin layer (I) that the laminate has, and the hardening of the object to be sealed and at least the peripheral portion of the object to be sealed In the step of covering the aforementioned adhesive surface of the resin layer (I) with a thermosetting sealing material, the step of thermosetting the aforementioned sealing material to form a hardened sealing body containing the aforementioned object to be sealed is also performed by making the curable resin layer (I) ) is thermally hardened to form a hardened resin layer, thereby producing a hardened sealing body with a hardened resin layer. [10] A method of manufacturing a cured sealing body with a cured resin layer, which is a method of manufacturing a cured sealing body using the anti-warping laminate described in [8] above, characterized by comprising: A part of the adhesive surface of the curable resin layer (I) that the laminate has, the step of placing the object to be sealed, the step of irradiating energy rays to harden the energy ray curable resin layer (X2), and the step of sealing the aforementioned The step of coating the target object with the aforementioned adhesive surface of the curable resin layer (I) on at least the peripheral portion of the aforementioned sealed target object with a thermosetting sealing material, and thermosetting the aforementioned sealing material to form the aforementioned sealing target. Simultaneously with the hardened sealing body of the object, the curable resin layer (I) is also thermally cured to form a hardened resin layer (I'), thereby producing a hardened sealed body with a hardened resin layer. [Effect of Invention]

According to the content of the present invention, in order to provide a cured resin layer that can serve as a warpage-resistant layer of a cured seal formed by the sealing process while fixing an object to be sealed on the surface of the curable resin layer for sealing process, Also, an anti-warp laminate capable of preventing poor peeling of a curable resin layer and a support layer, and a method for producing a cured sealing body using the anti-warp laminate.

First, terms used in this specification will be explained. In this specification, the method of judging whether the target layer is a "non-expandable layer" is that after performing the expansion treatment for 3 minutes, if the volume change rate before and after the treatment is calculated according to the following formula, it is less than 5%. The layer was judged as "non-expandable layer". In addition, when the above-mentioned volume change rate is 5% or more, the layer is judged as an "expandable layer". ・Volume change rate (%)={(volume of the aforementioned layer after treatment-volume of the aforementioned layer before treatment)/volume of the aforementioned layer before treatment}×100 Also, "expanding treatment" means, for example, in the case of a layer containing heat-expandable particles, it is sufficient to heat-treat for 3 minutes at the expansion initiation temperature (t) of the heat-expandable particles. Moreover, when expandable particle|grains expand by foaming, the said expansion start temperature (t) is also called a foaming start temperature (T2).

In this specification, the term "active ingredient" refers to a component in which a diluting solvent is excluded from the components included in the target composition. In the present specification, the mass average molecular weight (Mw) is a value measured using gel permeation chromatography (GPC) in terms of standard polystyrene, specifically, a value measured based on the method described in Examples. In this specification, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also the same. In this specification, the lower limit and the upper limit described in stages in a preferable numerical range (for example, the range of content etc.) are each independent and combinable. For example, the description of "preferably 10-90, more preferably 30-60" can be combined with "preferably lower limit (10)" and "better upper limit (60)", and Those who are "10-60".

In this specification, "energy ray" refers to an electromagnetic wave or a charged particle ray having energy quanta, for example, ultraviolet rays, radiation rays, electron rays, and the like. Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp (Fusion Light), a xenon lamp, a fluorescent lamp, or an LED lamp as an ultraviolet light source. Electron beams are those that irradiate electrons generated using electron beam accelerators, etc. In this specification, "energy ray curable" means having the property of being cured by irradiation of energy ray, and "non-energy ray curable" means having the property of being cured by irradiating energy ray.

In this specification, the lowest temperature at which the hardening of the curable resin can be completed within 2 hours is also referred to as the "minimum hardening temperature". In this specification, "hardening complete" means that when a sample is measured using a differential scanning calorimeter, the peak attributable to the hardening reaction disappears from the temperature characteristic curve.

Hereinafter, an embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described. [Laminate for anti-warpage] The laminate for anti-warpage according to one aspect of the present invention has a curable resin layer (I) including a thermosetting resin layer (X1), and a supporting curable resin layer (I). ) of the supporting layer (II). In addition, in the following description, the warpage-resistant laminate is also referred to as a "laminate". The thermosetting resin layer (X1) is preferably directly laminated on the support layer (II). The curable resin layer (I) is an adhesive surface with adhesive properties. 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 adhesive layer (V) contains thermally expandable particles. The curable resin layer (I), the adhesive layer (V), and the substrate (Y) are arranged in this order, and the aforementioned adhesive surface of the curable resin layer (I) is arranged on the adhesive layer ( V) is the opposite side. The minimum curing temperature (T ₁ ) at which the curing of the curable resin layer (I) is completed within 2 hours to form the cured resin layer (I') is lower than the temperature at which the thermally expandable particles start to foam (T ₂ ). .

＜Contents of anti-warping laminate＞ The configuration of the anti-warp laminate of this embodiment will be described using the drawings. FIGS. 1 to 5 are cross-sectional schematic views of the warpage-preventing laminate according to the first to fifth aspects of the present invention. In addition, in the laminates of the following first to fifth aspects, on the adhesive surface of the adhesive layer (V1) attached to the support not shown in the drawings, and the second layer of the curable resin layer (I) 1 The surface (the surface on the opposite side to the support layer (II)) may further have a composition of a laminate release material from the viewpoint of protecting the surface of the curable resin layer (I) or the support layer (II). Moreover, this release material can be peeled off and removed when using the laminated body for anti-warpage.

[First Aspect: Anti-warping Laminate] The anti-warping laminate of the first aspect of the present invention is, for example, the laminates 1a and 1b shown in FIG. 1 . The laminates 1a and 1b are provided with: a support layer (II) having a base material (Y) and an adhesive layer (V1), and a curable resin layer (I); and having a base material (Y), and a curable resin layer (I) is the constituent content of direct lamination. In the following description, the surface of the curable resin layer (I) opposite to the support layer (II) is also referred to as a "first surface", and the surface on the support layer (II) side is also referred to as a "second surface". The first surface of the curable resin layer (I) is an adhesive surface having a specific adhesive force, and when the object to be sealed is placed, the object to be sealed can be fixed with this adhesive force. In addition, in the laminates 1a and 1b, the adhesive surface of the adhesive layer (V1) is attached to a support not shown in the drawings.

In the support layer (II), at least one of the base material (Y) and the adhesive layer (V1) contains heat-expandable particles and has expansibility. In the laminated body 1a of FIG. 1(a), the base material (Y) has an expandable base material layer (Y1) containing thermally expandable particles. The base material (Y), like the laminated body 1a shown in Figure 1(a), can be a base material consisting only of a single layer formed by an expandable base material layer (Y1), or as shown in Figure 1(b) In general, the laminate 1b is a substrate having a multilayer structure having an expandable base material layer (Y1) and a non-expandable base material layer (Y2). Also, in the warpage-resistant laminate of the first aspect, when using a base material (Y) having an expandable base material layer (Y1) and a non-expandable base material layer (Y2), as shown in Figure 1(b) As shown, the non-expandable base layer (Y2) is laminated on the surface of the adhesive layer (V1), and the expandable base layer (Y1) is laminated on the surface of the non-expandable base layer (Y2). Content is better.

The laminated body 1a shown in Fig. 1(a) undergoes expansion treatment (hereinafter, also referred to as "heat expansion treatment") by heating, so that the thermally expandable particles contained in the expandable base material layer (Y1) are expanded, and in the Since the surface of the base material (Y) is uneven, the contact area with the cured resin layer formed by curing the curable resin layer (I) is reduced. In addition, in the following description, a layer formed by curing the curable resin layer is referred to as a cured resin layer (I'). At this time, the adhesive surface of the adhesive layer ( V1 ) is attached to a support (not shown in the drawings). The adhesive layer (V1) and the support are attached in a very close manner, so even if a force that can form unevenness occurs on the surface of the expandable base material layer (Y1) on the adhesive layer (V1) side, it is easy to The counterbalancing force is produced by the adhesive layer (V1). Therefore, unevenness is not easily formed on the surface of the substrate (Y) on the side of the adhesive layer (V1). As a result, in the laminated body 1a, at the interface P between the base material (Y) of the support layer (II) and the cured resin layer (I'), the whole can be easily separated by using a little force. In addition, since the adhesive layer (V1) of the laminated body 1a is formed using an adhesive composition that can improve the adhesive force to the support, separation can also be more easily formed at the interface P. In the following description, the interface between the curable resin layer (I) and the support layer (II) may also be referred to as "interface P".

Also, from the viewpoint of suppressing the stress generated by the heat-expandable particles from being transmitted to the side of the adhesive layer (V1), like the laminate 1b shown in FIG. ) and non-expandable substrate layer (Y2) are preferred. The stress generated by expansion of the thermally expandable particles of the expandable base material layer (Y1) is suppressed by the non-expandable base material layer (Y2), so it is difficult to transmit to the adhesive layer (V1). Therefore, it is difficult to form unevenness on the surface of the support body side of the adhesive layer (V1), so that the adhesion between the adhesive layer (V1) and the support body hardly changes before and after thermal expansion treatment, and can maintain good Adhesion. Therefore, unevenness is easily formed on the surface of the curable resin layer (I) side of the expandable base material layer (Y1), as a result, the expandable base material layer (Y1) of the support layer (II) and the cured resin layer (I) ') interface P, as long as a little force can be used to make it easy to separate the whole.

Also, like the laminated body 1b shown in Figure 1(b), the expansive base material layer (Y1) and the curable resin layer (I) are directly laminated, and the adhesive layer (V1) is laminated on the non- The configuration on the surface of the expandable base material layer (Y2) opposite to the curable resin layer (I) is preferable. In addition, between the expandable base material layer (Y1) and the non-expandable base material layer (Y2), for the purpose of bonding the two, either an adhesive layer or an anchor layer may be provided, or they may be directly laminated.

[Second Aspect: Anti-warping Laminate] The anti-warp laminates of the second aspect of the present invention are, for example, the anti-warp laminates 2a and 2b shown in FIG. 2 . The laminated body 2a, 2b has: the adhesive layer that the support layer (II) has, is to have the first adhesive layer (V1-1) and the second adhesive layer (V1-2), and the first adhesive layer (V1-1) and the second adhesive layer (V1-2) sandwich the substrate (Y), and the adhesive surface of the second adhesive layer (V1-2) is directly laminated with the curable resin layer (I) its composition. Hereinafter, each adhesive layer in the case where the support layer (II) has a plurality of adhesive layers, and the adhesive layer in the case where the support layer (II) has a single adhesive layer is also collectively referred to as an adhesive layer (V). . Also, in the warpage-resistant laminate of the second aspect, the adhesive surface of the first adhesive layer (V1-1) is attached to a support not shown in the drawings.

In the warpage-resistant laminate of the second aspect, the substrate (Y) preferably has an expandable substrate layer (Y1) containing heat-expandable particles. The base material (Y), like the laminated body 2a shown in Figure 2(a), can be a base material consisting only of a single layer formed by the expandable base material layer (Y1), or as shown in Figure 2(b) As shown in the laminated body 2b, it may be a base material having a multilayer structure formed of an expandable base material layer (Y1) and a non-expandable base material layer (Y2).

Also, as described above, from the viewpoint of being a laminate that can maintain good adhesion between the first adhesive layer (V1-1) and the support before and after the thermal expansion treatment, as shown in FIG. 2(b) Generally, the substrate (Y) preferably has an expandable substrate layer (Y1) and a non-expandable substrate layer (Y2). Also, in the warpage-resistant laminate of the second aspect, when using a base material (Y) having an expandable base material layer (Y1) and a non-expandable base material layer (Y2), as shown in FIG. 2(b) As shown, the first adhesive layer (V1-2) is laminated on the surface of the expandable base material layer (Y1) with the second adhesive layer (V1-2) and the surface of the non-expandable base material layer (Y2). -1) The content of the composition is preferable.

In the laminated body of the second aspect, thermally expandable particles in the expandable base material layer (Y1) constituting the base material (Y) can be expanded through heat expansion treatment, and the heat-expandable particles on the surface of the expandable base material layer (Y1) can be expanded. Form bumps. Subsequently, by pressing the second adhesive layer (V1-2) on the surface of the expansive base material layer (Y1) to generate concavities and convexities, the adhesive surface of the second adhesive layer (V1-2) can also be formed Concavo-convex, thus reducing the contact area between the second adhesive layer (V1-2) and the cured resin layer (I'). As a result, the interface P between the second adhesive layer (V1-2) of the support layer (II) and the cured resin layer (I') can be easily separated as a whole with only a little force. In addition, in the laminated body of the second aspect, on the interface P, the entire laminated body can be easily separated by using only a little force, and the expansion of the base material (Y) included in the support layer (II) It is preferable that the permanent base material layer (Y1) and the second adhesive layer (V1-2) have a structure of direct lamination.

[Third Aspect: Anti-warping Laminate] The warpage-resistant laminate of the third aspect of the present invention is, for example, the warpage-resistant laminate 3 shown in FIG. 3 . The laminated body 3 shown in Fig. 3 has: on the surface side of one side of the substrate (Y), a first adhesive layer (V1) with a non-expandable adhesive layer, on the other side of the substrate (Y) On the surface side of the side, there is a supporting layer (II) of the second adhesive layer (V2) of the expandable adhesive layer containing thermally expandable particles, and the second adhesive layer (V2) and curable resin layer (I) are The composition of direct lamination. In laminate 3, the adhesive surface of the first adhesive layer (V1) is attached to a support not shown in the drawings. Moreover, it is preferable that the base material (Y) which the laminated body 3 of this 3rd aspect has consists of a non-expandable base material layer (Y2). In the laminated body 3 of the third aspect, thermally expandable particles in the second adhesive layer (V2) of the expandable adhesive layer are expanded through thermal expansion treatment, and the heat-expandable particles in the second adhesive layer (V2) are expanded. The unevenness is formed on the surface, so the contact area between the second adhesive layer (V2) and the curable resin layer (I) can be reduced. On the other hand, on the surface of the substrate (Y) side of the first adhesive layer (V1), since it is laminated on the substrate (Y), it is difficult to form unevenness. Therefore, it is easy to form irregularities on the surface of the curable resin layer (I) side of the second adhesive layer (V2) during thermal expansion treatment, and as a result, the second adhesive layer (V2) of the support layer (II) The interface P with the cured resin layer (I') can be easily separated as a whole with a little force.

[Fourth Aspect: Anti-warping Laminate] The warpage-resistant laminate of the fourth aspect of the present invention is, for example, the warpage-resistant laminate 4 shown in FIG. 4 . The laminated body 4 shown in FIG. 4 is sequentially provided with a non-expandable adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I). In the laminate 4, the curable resin layer (I) is composed of a first thermosetting resin layer (X1-1) located on the side of the base material (Y), and a first thermosetting resin layer (X1-1) located on the side opposite to the base material (Y). The curable resin layer (I) of the second thermosetting resin layer (X1-2) is constituted. Both the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2) are non-expandable. Among them, the second thermosetting resin layer (X1-2) has higher surface adhesion than the first thermosetting resin layer (X1-1). In the laminate 4, the curable resin layer (I) is composed of two thermosetting resin layers, and components having mutually different properties can be used. For example, for the curable resin layer on the opposite side of the support layer (II), a thermosetting resin layer containing a composition with higher adhesiveness can be selected, and the curable resin layer on the side of the support layer (II) can be selected to support The separability of layer (II) is a more favorable composition.

[Fifth Aspect: Anti-warping Laminate] The warpage-resistant laminate of the fifth aspect of the present invention is, for example, the warpage-resistant laminate 5 shown in FIG. 5 . The laminated body 5 shown in FIG. 5 has a composition in which a non-expandable adhesive layer (V1), an expandable base material layer (Y1), and a curable resin layer (I) are sequentially laminated. In the laminate 5, the curable resin layer (I) is composed of a thermosetting resin layer (X1-1) located on the side of the base material (Y), and an energy line located on the side opposite to the base material (Y). The curable resin layer (I) of the curable resin layer (X2) is constituted. Both the first thermosetting resin layer (X1-1) and the energy ray curable resin layer (X2) are non-expandable. In the laminated body 5, the curable resin layer (I) is divided into an energy ray curable resin layer (X2) and a thermosetting resin layer (X1-1), which can use mutually different components. For example, on the side opposite to the support layer (II), an energy-curable resin layer formed of an energy ray-curable composition having a high adhesive force and which is easy to adjust is arranged, and on the side of the support layer (II), an energy-curable resin layer may be arranged. A thermosetting resin layer having better separability with the sealing material described later.

[Applications of warpage-resistant laminates] The anti-warp laminate of the present embodiment is used for placing an object to be sealed on the surface of the curable resin layer, covering the object to be sealed with a sealing material, and heat at least the peripheral portion of the object to be sealed. A method of hardening the sealing material on the surface of the curable resin layer to produce a hardened sealing body including a hardened sealing body of an object to be sealed. Moreover, the specific aspect about the method of manufacturing the cured sealing body using the laminated body for warping is mentioned later.

For example, when using the manufacturing method described in Patent Document 1, the object to be sealed should be placed on the adhesive surface of an adhesive laminate such as a general wafer mount tape, and then the object to be sealed and the object to be sealed should be covered with a sealing material. The adhesive surface of the peripheral part is heat-hardened by sealing material to obtain a hardened sealing body. When the sealing material is thermally hardened, the sealing material will be subjected to shrinkage stress, but since the adhesive laminate is fixed on the support body, the stress of the sealing material will be suppressed. However, the hardened sealing body obtained by separating the support body and the adhesive laminate cannot easily suppress the stress that tends to shrink. Therefore, in the separated hardened sealing body, the difference in shrinkage stress tends to occur due to the difference in the amount of the sealing material between the surface side where the object to be sealed exists and the surface side opposite to it. This difference in shrinkage stress is the cause of warping of the hardened seal. Also, from the viewpoint of productivity, the hardened sealing body after heating is generally separated from the support body and the adhesive laminate more than in a state with a certain degree of heat. Therefore, after separation, the sealing material is still in the process of hardening, and shrinks with natural cooling, so that the hardened sealing body will be in a state where warpage is more likely to occur.

On the other hand, when the anti-warp laminate of one aspect of the present invention is used, a cured sealing body that effectively suppresses warpage can be obtained for the following reason. That is, in the anti-warp laminate according to one aspect of the present invention, the object to be heat-sealed is placed on the surface of the curable resin layer, covered with a sealing material, and when the sealing material is thermally cured, it is also thermally cured. The resin layer is thermally hardened. At this time, since the thermosetting resin layer is provided on the surface side of the object to be sealed, where the amount of the sealing material is low and the shrinkage stress caused by the hardening of the sealing material is small, the thermosetting resin layer will be activated during thermosetting. shrinkage stress. As a result, it is presumed that the difference in shrinkage stress between the two surfaces of the cured sealing body can be reduced, and a cured sealing body capable of effectively suppressing warpage can be obtained.

Also, the thermosetting resin layer capable of suppressing warping of the cured sealing body is one capable of forming a cured resin layer through thermosetting. That is, using the warpage-resistant laminated body of one aspect of the present invention, the hardened resin layer can be formed on one side surface of the hardened sealing body at the same time through the above-mentioned sealing step, so the step of forming the hardened resin layer can be omitted, and the Improve productivity.

In addition, in the anti-warp laminate of one aspect of the present invention, at least one of the base material (Y) and the adhesive layer (V) contained in the support layer (II) contains thermally expandable particles, and is hardened. The minimum curing temperature (T ₁ ) at which the curing of the permanent resin layer (I) is completed within 2 hours to form the cured resin layer (I') is lower than the foaming initiation temperature (T ₂ ) of the above-mentioned thermally expandable particles . Therefore, when the above-mentioned heat-expandable particles are expanded by heating, it is possible to prevent the occurrence of poor peeling between the curable resin layer (I) and the support layer (II).

<Physical properties of the laminate> (Minimum curing temperature (T ₁ ) of the curable resin layer (I)) In the warpage-resistant laminate according to one aspect of the present invention, the substrate contained in the support layer (II) ( At least one of Y) and the adhesive layer (V) contains heat-expandable particles, and the hardening of the curable resin layer (I) is completed within 2 hours to form the lowest hardening temperature ( _T1 ') of the hardened resin layer (I'). ) is lower than the foaming initiation temperature (T ₂ ) of the above-mentioned heat-expandable particles. Therefore, thermal expansion of the heat-expandable particles can be suppressed during heat-hardening of the curable resin layer. 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, thereby preventing the occurrence of poor peeling between the two. One of the reasons why the peeling defect is suppressed is, although not limited to this content, the following reason is presumed. During heat curing of the curable resin layer, the heat-expandable particles thermally expand to generate irregularities at the interface with the curable resin layer, and the curable resin layer is also hardened to be firmly fixed to the irregularities. Therefore, even when the thermally expandable particles are heated and expanded after the curable resin layer is cured, the peelability from the cured resin layer is not reduced. On the other hand, in the laminated body of this embodiment, the thermal expansion of the heat-expandable particles is suppressed during the heat-hardening period of the curable resin layer, so it is estimated that when the heat-expandable particles are thermally expanded after the hardening of the curable resin layer is completed, even Even when the interface with the cured resin layer has sufficient unevenness, the peelability between the two can be ensured.

The difference between the minimum curing temperature (T ₁ ) of the curable resin layer (I) and the foaming initiation temperature (T ₂ ) of the heat-expandable particles (T ₂ -T ₁ ) is preferably 20-100°C, more preferably 20-90°C, particularly preferably 20-80°C. When the temperature difference T ₂ -T ₁ is in the above temperature range, a sufficient temperature difference can be set, and as a result, in addition to easily suppressing the peeling failure phenomenon, it can also increase the freedom of choice of the physical properties of the thermally expandable microparticles or materials.

(Adhesion to the first surface of the curable resin layer (I)) The laminate according to one aspect of the present invention has adhesiveness on the surface (first surface) on which the object to be sealed is placed on the curable resin layer (I) from the viewpoint of good adhesion to the object to be sealed. Whichever is better. The adhesive force of the first surface of the curable resin layer (I) is as follows: attach the above-mentioned first surface to a glass plate at a temperature of 70°C, under the conditions of a temperature of 23°C, a peeling angle of 180°, and a peeling speed of 300mm/min , the value measured when the above-mentioned curable resin layer is peeled off is preferably 1.7N/25mm or more, more preferably 2.3N/25mm or more, particularly preferably 3.0N/25mm or more, most preferably 4.0N/25mm or more , and preferably less than 20N/25mm, more preferably less than 15N/25mm, particularly preferably less than 10N/25mm. When the adhesive force of the first surface of the curable resin layer (I) is 1.7 N/25mm or more, when the object to be sealed is fixed on the surface of the curable resin layer (I), the positional displacement of the object to be sealed can be easily prevented. When the adhesive force of the first surface of the curable resin layer (I) is 20N/25mm or less, it will be easier to select the material of the curable resin layer (I).

(Shear force of curable resin layer (I)) When the laminated body of one aspect of the present invention is used as an object to be sealed, it is preferable that the curable resin layer (I) has an appropriate shearing force from the viewpoint of maintaining the object to be sealed well. Specifically, the shear strength of the adherend for measurement of the curable resin layer (I) is that a silicon wafer (mirror surface) with a thickness of 350 μm and a size of 3 mm×3 mm is used as the adherend for measurement above at a temperature of 70° C. , under the conditions of 130gf and 1 second, the mirror surface of the aforementioned measuring object to be attached is pressed and attached to the aforementioned hardening resin layer, and the value when measuring at a speed of 200μm/s is preferably 20N/(3mm× 3mm) or more, more preferably 25N/(3mm×3mm), especially preferably 30N/(3mm×3mm) or more, and preferably less than 100N/(3mm×3mm), more preferably 90N/(3mm×3mm) )the following. When the shear strength of the adherend for measurement of the curable resin layer (I) is 20N/(3mm×3mm) or more, fix the object to be sealed on the surface of the curable resin layer (I), and then cover and seal it with a sealing material It is easy to prevent the position deviation or inclination of the sealing object caused by the flow of the sealing material. Moreover, when the said shear strength is 100 N/(3mm*3mm) or less, selection of the material of curable resin layer (I) becomes easier.

(Adhesion of thermosetting resin layer (X1)) In the laminated body of an aspect of the present invention, the individual adhesive force of the thermosetting resin layer (I) 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. 25mm, the best is 0.4-6.0N/25mm, the best is 0.5-4.0N/25mm. Like the laminated body 4 shown in Figure 4, when having the first thermosetting resin layer (X1-1) and the second thermosetting resin layer (X1-2), it is better to have the above-mentioned adhesive force respectively , especially the adhesive strength of the second thermosetting resin layer (X1-2) is preferably higher than the adhesive strength of the first thermosetting resin layer (X1-1). When the adhesive force of the second thermosetting resin layer (X1-2) is higher than that of the first thermosetting resin layer (X1-1), the object to be sealed can be fixed to the curable resin more reliably. The first surface of layer (I).

(Adhesion of energy ray curable resin layer (X2)) In the laminated body of an aspect of the present invention, the independent adhesive force of the energy ray curable resin layer (X2) at room temperature (23°C) is preferably 0.1-10.0N/25mm, more preferably 0.2-8.0N /25mm, the best is 0.4-6.0N/25mm, the best is 0.5-4.0N/25mm.

(Adhesive force of adhesive layer (V)) In the laminate of one aspect of the present invention, the adhesive layer (V) (the first adhesive layer (V1) and the second adhesive layer (V2)) that the support layer (II) has at room temperature (23°C) ) is preferably 0.1-10.0N/25mm, more preferably 0.2-8.0N/25mm, particularly preferably 0.4-6.0N/25mm, most preferably 0.5-4.0N/25mm. In addition, in the following description, regardless of whether the adhesive layer is single or plural, the adhesive layer positioned on the side of the curable resin layer (I) is also referred to as the first adhesive layer, and the adhesive layer positioned on the side opposite to the curable resin layer The layer is also referred to as the second adhesive layer. The support layer (II) has the first adhesive layer (V1-1) or (V1), and when the second adhesive layer (V1-2) or (V2), the first adhesive layer (V1-1) or ( V1), the adhesive force with the second adhesive layer (V1-2) or (V2) is preferably in the above-mentioned range, but it improves the adhesion with the support and can be easily separated at the interface P to form a whole From the point of view, the adhesive force of the first adhesive layer (V1-1) or (V1) attached to the support is higher than the adhesive force of the second adhesive layer (V1-2) or (V2) for better.

(Measurement of Adhesion on the First Surface of Curable Resin Layer (I)) In this case specification, the adhesive force of the 1st surface of curable resin layer (I) is measured in the following procedure. First, a warpage-resistant laminate including a curable resin layer (I) and a support layer (II) was cut out to a width of 25 mm x a length of 250 mm (250 mm in the MD direction) to obtain a primary sample. In addition, the object to be attached was a prepared glass plate (float glass 3 mm (JIS R3202 product) manufactured by U-KOU Shokai Co., Ltd.). Using a laminator device (manufactured by Taisei Laminator Co., Ltd., Model VA-400), a glass plate was directly bonded to the first surface of the curable resin layer (I) to prepare a test piece. At this time, the conditions were set such that the drum temperature was 70° C. and the sticking speed was 0.2 m/min. The test piece prepared in this way was left to stand for 24 hours in an environment of 23°C and 50% RH (relative humidity), and in the same environment, it was measured using a tensile load based on JIS Z 0237:2000. Machine (manufactured by AANDD, TENSILON), under the conditions of peeling angle 180°, peeling speed 300mm/min, and peeling temperature 23°C, measure the adhesive force when the test piece is peeled from the glass plate, and use the measured value as the curable resin layer (I) Adhesion of the first surface.

(Measurement of shear force of curable resin layer (I)) In the present specification, the shearing force of the curable resin layer (I) is measured in the following procedure. First, a 3 mm x 3 mm silicon wafer having a mirror surface and a thickness of 350 μm was used as an adherend for measurement. Subsequently, at a temperature of 70° C., under the conditions of 130 gf and 1 second, the mirror surface of the adhered body for the above-mentioned measurement was pressed and pasted to the curable resin layer (I ) of the first surface. Then, the shear force was measured at a speed of 200 μm/s using a universal adhesion tester (manufactured by Nordson-at Technology Co., Ltd., DAGE4000).

(Measurement of Adhesive Strength of Adhesive Layer (V), Thermosetting Resin Layer (X1), and Energy Ray Curing Resin Layer (X2)) Adhesive layer (V), thermosetting resin layer (X1), or energy ray-curing resin layer formed by laminating adhesive tape (manufactured by Linde Co., Ltd., product name "PL-SHIN") on a release film (X2) surface. Subsequently, the surface of the adhesive layer (V), the thermosetting resin layer (X1) or the energy ray curable resin layer (X2) exposed after peeling off the release film is attached to the glass plate (U- Float glass 3 mm (JIS R3202 product) made by KOU Shokai Co., Ltd. At this time, the sticking temperature of the 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. Subsequently, the above-mentioned glass plate with each layer was left to stand for 24 hours at 23°C and 50% RH (relative humidity). Tensile peeling method, under the condition of a tensile speed of 300mm/min, peel the adhesive layer (V), thermosetting resin layer (X1) or energy ray curable resin layer (X2) together with the adhesive tape from the above glass plate, Measure its adhesion at 23°C.

(Peel force before expansion treatment (F ₀ )) The curable resin layer (I) can fully fix the object to be sealed before it is cured and before expansion treatment, and does not adversely affect the sealing operation , the higher the adhesion between the support layer (II) and the curable resin layer (I), the better. Based on the above point of view, in the laminated body of one aspect of the present invention, before the curable resin layer (I) is cured and before thermal expansion treatment, the interface P between the support layer (II) and the curable resin layer (I) The peel force (F ₀ ) at the time of separation is preferably at least 100 mN/25 mm, more preferably at least 130 mN/25 mm, particularly preferably at least 160 mN/25 mm, and preferably at most 50,000 mN/25 mm. In addition, the peel force (F ₀ ) is a value measured by the following measurement method. (Measurement of Peeling Force (F ₀ )) After the laminate was left to stand for 24 hours at 23°C and 50% RH (relative humidity), the support layer (II) side of the laminate was placed through the adhesive layer Attached to a glass plate (floating glass 3 mm (JIS R3202 product) manufactured by U-KOU Shokai Co., Ltd.). In addition, an adhesive tape (manufactured by Linde Co., Ltd., product name "PL-SHIN") was pasted on the first surface side of the laminate. Next, the end of the glass plate to which the laminate was attached was fixed to a lower jig of a universal tensile testing machine (manufactured by Oriental Technology Co., Ltd., product name "TENSILON UTM-4-100"). Subsequently, in order to form peeling at the interface P between the support layer (II) and the curable resin layer (I) of the laminate, the curable resin layer (I) attached to the laminate was fixed using the upper clamp of the universal tensile testing machine. The end of the adhesive tape. Then, in the same environment as above, based on JIS Z 0237: 2000, use the 180° stretching peeling method at a stretching speed of 300mm/min to put the curable resin layer (I) and the adhesive tape, The peel force measured when the interface P is peeled from the support layer (II) is defined as "peel force (F ₀ )".

(Peel force after expansion treatment (F ₁ )) In the laminated body of an aspect of the present invention, after expansion treatment, the support layer (II), the curable resin layer (I), or the curable resin layer (I) The interface P of the cured resin layer (I') after curing can be easily separated as a whole with a little force. Among them, in the laminated body of one aspect of the present invention, after the hardened resin layer (I) is hardened to form the hardened resin layer (I'), after expansion treatment, the support layer (II) and the hardened resin layer (I') ') The peeling force (F ₁ ) when the interface P forms separation is usually 2,000mN/25mm or less, preferably 1,000mN/25mm or less, more preferably 500mN/25mm or less, more preferably 150mN/25mm or less, especially The best is below 100mN/25mm, the best is below 50mN/25mm, and the most optimal is 0mN/25mm. When the peeling force (F ₁ ) is 0 mN/25 mm, it includes the case where the peeling force cannot be measured because the peeling force is too low even if it is measured. In addition, the peel force (F ₁ ) is a value measured by the following measurement method.

(Measurement of Peeling Force (F ₁ )) The support layer (II) side of the laminate was attached to a glass plate (3 mm float glass (JIS R3202 product) manufactured by U-KOU Shokai Co., Ltd.) through an adhesive layer. Next, the above-mentioned glass plate and laminate were heated at 130° C. for 2 hours to harden the curable resin layer (I) to form a curable resin layer (I′). Like the laminated body 4 in Figure 4, when the curable resin layer (I) includes the energy ray curable resin layer (X2), after the thermosetting resin layer (X1-1) is thermally cured, irradiation can make the energy ray curable The energy ray (in the case of ultraviolet rays, illuminance 215mW/cm ² , light intensity 187mJ/cm ² , irradiated 3 times) for hardening the resin layer (X2) hardens the energy ray-curable resin layer (X2). Subsequently, the heat-expandable particles contained in the support layer (II) are expanded. Specifically, for the glass plate to which the laminate is attached, heat at 240°C for 3 minutes, so that the heat-expandable particles in the expandable substrate layer (Y1) or expandable adhesive layer (V2) of the laminate swell. Then, stick an adhesive tape (manufactured by Linde Co., Ltd., product name "PL-SHIN") on the first surface side of the laminate, and follow the same conditions as the above-mentioned measurement of the peeling force (F ₀ ). When the interface P of the support layer (II) and the cured resin layer (I′) peels, the peeling force measured is referred to as "peeling force (F ₁ )". In addition, in the measurement of the peeling force (F ₁ ), when the end of the adhesive tape attached to the hardened resin layer (I') of the laminate is fixed using the upper grip of the universal tensile testing machine, the The cured resin layer (I') is completely separated. If the measurement is carried out without fixation, the measurement is terminated, and the peeling force (F ₁ ) at this time is "0mN/25mm".

(Tensile Strength Value of Substrate (Y)) The substrate (Y) included in the support layer (II) is a non-adhesive substrate. In one aspect of the present invention, the determination of whether it is a non-adhesive base material is when the tensile strength value measured on the basis of JIS Z 0237: 1991 for the surface of the target base material is less than 50mN/5mmφ , then it is judged that the substrate is "non-adhesive substrate". Moreover, when the above-mentioned tensile strength value is 50 mN/5 mmφ or more, the base material is judged as an "adhesive base material". The support layer (II) used in one aspect of the present invention has a tensile strength value on the surface of the substrate (Y), usually less than 50mN/5mmφ, preferably less than 30mN/5mmφ, More preferably, it is less than 10mN/5mmφ, and most preferably, it is less than 5mN/5mmφ. The tensile strength value on the surface of the substrate (Y) is a value measured by the following measurement method. (Measurement of Tensile Strength Value) The substrate to be measured was cut into a square of 10 mm on one side, and then left to stand in an environment of 23° C. and 50% RH (relative humidity) for 24 hours to obtain a test sample. In an environment of 23°C and 50% RH (relative humidity), use a viscosity tester (manufactured by Nippon Special Sekki Co., Ltd., product name "NTS-4800") to measure the surface of the test sample according to JIS Z0237:1991 the tensile strength value. Specifically, after contacting the surface of the test sample with a stainless steel detector with a diameter of 5mm for 1 second and a contact load of 0.98N/cm ² , then measure the speed of the detector at a speed of 10mm/second from the test sample. The force necessary for the surface to leave, and the resulting value, is taken as the tensile strength value of the test sample.

Next, the content of each layer constituting the anti-warp laminate of one aspect of the present invention will be described. ＜Curing resin layer (I)＞ The anti-curling laminate of one aspect of the present invention has a curable resin layer (I) including a thermosetting resin layer (X1). Since the shrinkage stress difference between the two surfaces of the cured sealing body can be reduced as the sealing material formed by curing the curable resin layer (I) hardens, warping of the resulting cured sealing body can be suppressed. The curable resin layer (I) is cured to form a cured resin layer (I'). The cured resin layer (I') is formed on one side surface of the obtained cured sealing body.

As mentioned above, the minimum curing temperature (T ₁ ) at which the curing of the curable resin layer (I) is completed within 2 hours to form the cured resin layer (I') is higher than that of the thermally expandable particles contained in the support layer (II). The foaming initiation temperature (T ₂ ) is lower. These physical properties are mainly influenced by the thermosetting resin layer (X1) contained in the curable resin layer (I).

The storage modulus E' of the cured resin layer (I') at 23° C. is preferably 1.0×10 ⁷ from the viewpoint of obtaining a warpage-resistant laminate that suppresses warpage and has a hardened sealing body having a flat surface. Pa or more, more preferably 1.0×10 ⁸ Pa or more, particularly preferably 1.0×10 ⁹ Pa or more, most preferably 5.0×10 ⁹ Pa or more, and preferably 1.0×10 ¹³ Pa or less, more preferably 1.0×10 9 Pa or more. 10 ¹² Pa or less, particularly preferably 5.0×10 ¹¹ Pa or less, most preferably 1.0×10 ¹¹ Pa or less.

The storage modulus E' of the cured resin layer (I') was measured in the following order. First, after laminating the curable resin layer (I) into a layer with a thickness of 200 μm, it is brought to the state where the curing is actually completed (measured using a differential scanning calorimeter, at 130°C, when the heat generation peak disappears) . In the case of thermosetting resin layers (X1), (X1-1), and (X1-2), put them in an oven under the atmosphere, heat the resin at 130°C for 2 hours, and heat The curable resin layer is thermally cured. In the case of including the energy ray curable resin layer (X2) and the thermosetting resin layer (X1-1), irradiate energy rays (in the case of ultraviolet rays, illuminance 215mW/cm ² , light intensity 187mJ/cm ² , and irradiate 3 times ) to harden the energy ray curable resin layer (X2), and then thermoset the thermosetting resin layer (X1-1) according to the above conditions. Then, using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), under the conditions of a test start temperature of 0°C, a test end temperature of 300°C, a heating rate of 3°C/min, a vibration frequency of 11 Hz, and an amplitude of 20 μm , At 23°C, the storage modulus E' of the cured resin layer formed was measured.

In the curable resin layer (I), the first surface of the surface opposite to the support layer has adhesiveness. Subsequently, the adhesive force is, as mentioned above, attach the above-mentioned first surface to the glass plate at a temperature of 70°C, and harden the above-mentioned surface under the conditions of a temperature of 23°C, a peeling angle of 180°, and a peeling speed of 300mm/min. The value measured when the permanent resin layer is peeled off is preferably 1.7N/25mm or more. In addition, in the present specification, in the measurement of the adhesive force of the curable resin layer (I), "sticking at a temperature of 70°C" means that the laminated body is bonded using a pressing body such as a pressure roller with a heating temperature of 70°C. Pressing on the glass plate, so that the laminate is attached to the glass plate. Though the above-mentioned 1st surface of curable resin layer (I) is loaded with sealing object, because the surface of curable resin layer (I) has above-mentioned adhesiveness, so have good adhesion with sealing object, When an object to be sealed such as a semiconductor wafer is placed on the above-mentioned first surface, it can prevent the object to be sealed from being tilted, and after the object to be sealed is placed, the position of the object to be sealed relative to the curable resin layer (I) deviates from the expected position, etc. .

Also, the shear strength of the adherend for measurement of the curable resin layer (I) is as follows: a silicon wafer (mirror surface) with a thickness of 350 μm and a size of 3 mm×3 mm is used as the adherend for measurement at a temperature of 70° C. Under the conditions of 130gf and 1 second, the mirror surface of the aforementioned measuring object to be attached is pressed and pasted on the aforementioned curable resin layer, and the value is measured at a speed of 200μm/s, which is preferably 20N/(3mm×3mm) above.

The adhesive force of the first surface of the curable resin layer (I), or the shear force of the adherend for measurement of the curable resin layer (I), can be composed of the thermosetting resin constituting the curable resin layer (I). The type or addition ratio of the components of the material or the energy ray curable resin composition is adjusted to the above-mentioned numerical range. Adhesive force or shearing force can be changed depending on the composition or addition ratio of the resin composition, and the shearing force can be changed depending on the overall composition of the curable resin layer (I), and the adhesive force can be, for example, , the acrylic polymer described later can be used as a polymer component, an epoxy resin can be used as a thermosetting component, a coupling agent can be used, and a higher value can be easily achieved. Also, the shearing force can easily reach a higher value when the content of the inorganic filler or crosslinking agent is increased, for example.

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

(Thermosetting resin layer (X1)) The thermosetting resin layers (X1), (X1-1), and (X1-2) are preferably formed of a thermosetting resin composition containing a polymer component (A) and a thermosetting component (B) . The thermosetting resin layers (X1), (X1-1), and (X1-2) are also collectively referred to as the thermosetting resin layer (X1). The curable resin composition may further contain one or more selected from the colorant (C), coupling agent (D), and inorganic filler (E). It is preferable to contain at least an inorganic filler (E) from the viewpoint of obtaining a warpage-resistant laminate that suppresses warpage and has a hardened sealing body having a flat surface.

The thermosetting resin layer (X1) is formed on the condition that the minimum curing temperature (T ₁ ) of the curable resin layer (I) satisfies the above relationship, and the curing of the thermosetting resin layer (X1) itself is completed within 2 hours The minimum curing temperature (T ₁ ) of the cured resin layer (I') is preferably lower than the foaming initiation temperature (T ₂ ) of the heat-expandable particles contained in the support layer (II). The minimum curing temperature (T ₁ ) of the thermosetting resin layer (X1) is preferably lower than 20°C or higher, more preferably lower than 25°C or higher relative to the foaming initiation temperature (T ₂ ) of the thermally expandable particles , especially preferably below 30°C. From the viewpoint of lowering the minimum hardening temperature, it is possible to add a hardening accelerator, increase the amount of hardening accelerator or crosslinking agent, or select a monomer that is easy to crosslink.

The thickness of the thermosetting resin layer (X1) may be within the same numerical range as the thickness of the curable resin layer (I). When the thermosetting resin layer (X1) consists of plural layers as shown in the thermosetting resin layers (X1-1) and (X1-2), the thickness of these layers should be equal to the total thickness of the curable resin layer. The thickness of (I) should just be in the same numerical range. Furthermore, among these layers, the thickness of the thinnest layer is preferably at least 10%, more preferably at least 20%, and most preferably at least 30% of the thickness of the thickest layer.

The curing start temperature of the thermosetting resin layer (X1) is preferably from 80 to 200°C, more preferably from 90 to 160°C, particularly preferably from 100 to 150°C. For the thermosetting resin layer (X1), use one whose hardening initiation temperature is lower than the expansion initiation temperature of the thermally expandable particles. The curing start temperature of the thermosetting resin layer (X1) is preferably lower than the expansion starting temperature of the thermally expandable particles by 5°C or less, more preferably 10°C or lower, particularly preferably 20°C or lower.

(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. The thermosetting resin composition contains the polymer component (A), so the formed thermosetting resin layer has flexibility and film-forming properties, and can make the laminate have good property retention. The mass average molecular weight (Mw) of the polymer component (A) is preferably more than 20,000, more preferably 20,000 to 3 million, more preferably 50,000 to 2 million, particularly preferably 100,000 to 1.5 million, most preferably 200,000 to 1 million.

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

The polymer component (A) is, for example, acrylic polymer, polyester, phenoxy resin, polycarbonate, polyether, polyurethane, polysiloxane, rubber-based polymer, and the like. These polymer components (A) may be used alone or in combination of two or more. Also, in this specification, although an acrylic polymer having an epoxy group or a phenoxy resin having an epoxy group has thermosetting properties, if these have a mass average molecular weight of 20,000 or more and have at least one Compounds with repeating units are considered to be included in the concept of polymer component (A).

Among these, the polymer component (A) preferably contains an acrylic polymer (A1). The content ratio of the acrylic polymer (A1) in the polymer component (A) is preferably 60 to 100 with respect to the total amount (100% by mass) of the polymer component (A) contained in the thermosetting resin composition. % by mass is more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass, most preferably 90 to 100% by mass.

(acrylic polymer (A1)) The mass average molecular weight (Mw) of the acrylic polymer (A1) is preferably from 20,000 to 3 million, more preferably from 100,000 to 1.5 million, 150,000 to 1.2 million for the best, and 250,000 to 1 million for the best.

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

Acrylic polymer (A1), for example, a polymer containing alkyl (meth)acrylate as the main component, specifically, an alkyl (meth)acrylate containing an alkyl group having 1 to 18 carbons (a1 ') (hereinafter, also referred to as "monomer (a1')") is preferably an acrylic polymer of the structural unit (a1) that contains the structural unit (a1), and is composed of a functional group-containing monomer ( a2') (hereinafter also referred to as "monomer (a2')") is more preferably an acrylic copolymer of the structural unit (a2). The acrylic polymer (A1) may be used alone or in combination of two or more. Moreover, when the acrylic polymer (A1) is a copolymer, the form of the copolymer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer.

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

From the viewpoint of improving the reliability of a cured sealing body with a cured resin layer produced by using a warpage-resistant laminate, the monomer (a1') contains (methyl) having an alkyl group having 1 to 3 carbon atoms. Alkyl acrylate is preferable, and methyl (meth)acrylate is more preferable. Based on the above point of view, the content of the structural unit (a11) produced by the alkyl (meth)acrylate having an alkyl group having 1 to 3 carbon atoms, relative to the total structural unit (100% by mass) of the acrylic polymer (A1) ), preferably 1 to 80% by mass, more preferably 5 to 80% by mass, particularly preferably 10 to 80% by mass.

In addition, the monomer (a1') is preferably an alkyl (meth)acrylate containing an alkyl group having 4 or more carbons, and an alkyl (meth)acrylate containing an alkyl group having 4 to 6 carbons is preferred. Preferably, it is more preferably to contain butyl (meth)acrylate. Based on the above point of view, the content of the structural unit (a12) produced by the alkyl (meth)acrylate having an alkyl group with 4 or more carbons (preferably 4 to 6, especially preferably 4) is relatively high relative to the content of the acrylic polymer The total structural units (100% by mass) of the substance (A1) are preferably 1 to 70% by mass, more preferably 5 to 65% by mass, particularly preferably 10 to 60% by mass.

The content of the structural unit (a1) is preferably at least 50% by mass, more preferably 50 to 99% by mass, particularly preferably 55 to 90% by mass, based on the total structural units (100% by mass) of the acrylic polymer (A1). % by mass, particularly preferably 60 to 90% by mass.

The monomer (a2') is preferably at least one selected from hydroxyl group-containing monomers and epoxy group-containing monomers. Also, the monomer (a2') may be used alone or in combination of two or more.

Hydroxyl-containing monomers, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxy(meth)acrylate, 3-hydroxy(meth)acrylate, 2-hydroxy(meth)acrylate Hydroxyalkyl (meth)acrylates such as esters, 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol, etc. Among them, the hydroxyl group-containing monomer is preferably hydroxyalkyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate is more preferable.

Monomers containing epoxy groups, such as epoxy (meth)acrylate, epoxy β-methyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, (meth)acrylates containing epoxy groups such as 3-epoxy ring-2-hydroxypropyl (meth)acrylate; chlorinated epoxy esters, allyl epoxy ethers, etc. Among these, epoxy group-containing monomers are preferably epoxy group-containing (meth)acrylates, and epoxy (meth)acrylates are more preferable.

The content of the structural unit (a2) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass, particularly preferably 10 to 45% by mass, based on the total structural units (100% by mass) of the acrylic polymer (A1). 40% by mass, preferably 10 to 30% by mass.

In addition, the acrylic polymer (A1) may have a structural unit derived from other monomers other than the above-mentioned structural units (a1) and (a2) within the range that does not impair the effect of the present invention. Other monomers, such as vinyl acetate, styrene, ethylidene, α-olefin, etc.

(thermosetting component (B)) The thermosetting component (B) has the function of thermosetting the formed thermosetting resin layer to form a hard cured resin layer, and is a compound having a mass average molecular weight of less than 20,000. The mass average molecular weight (Mw) of the thermosetting component (B) is preferably 10,000 or less, more preferably 100 to 10,000. The thermosetting component (B) is an epoxy compound (B1) containing a compound having an epoxy group and a thermosetting compound from the viewpoint of a warpage-resistant laminate that can suppress deformation and have a flat surface. The curing agent (B2) is preferable, and it is more preferable to contain a curing accelerator (B3) together with the epoxy compound (B1) and the thermosetting agent (B2).

Epoxy compounds (B1) such as polyfunctional epoxy resins, bisphenol A diepoxy ethers and their hydrides, o-cresol-novolac epoxy resins, dicyclopentadiene-type epoxy resins, biphenyl There are more than 2 functional groups in the molecule of bisphenol A epoxy resin, bisphenol F epoxy resin, phenylene skeleton epoxy resin, etc., and the mass average molecular weight is less than 20,000 epoxy compounds etc. The epoxy compound (B1) may be used alone or in combination of two or more.

The content of the epoxy compound (B1) is relative to the polymer component (A ) 100 parts by mass, preferably 1-500 parts by mass, more preferably 3-300 parts by mass, particularly preferably 10-150 parts by mass, most preferably 20-120 parts by mass.

The thermosetting agent (B2) functions as a curing agent for the epoxy compound (B1). The thermosetting agent is preferably a compound having two or more functional groups capable of reacting with epoxy groups in one molecule. The functional group can be phenolic hydroxyl group, alcoholic hydroxyl group, amine group, carboxyl group, acid anhydride and the like. Among these, phenolic hydroxyl groups, amino groups, or acid anhydrides are preferable, and phenolic hydroxyl groups , or an amino group is preferred, and an amino group is more preferred.

Phenol-based thermosetting agents having phenol groups include, for example, polyfunctional phenol resins, bisphenols, novolak-type phenol resins, dicyclopentadiene-type phenol resins, XYLOK-type phenol resins, aralkylphenol resins, and the like. An amine-based thermosetting agent having an amine group, for example, dicyandiamide and the like. These thermosetting agents (B2) may be used alone or in combination of two or more.

The content of the thermosetting agent (B2) is based on 100 parts by mass of the epoxy compound (B1) from the viewpoint of an adhesive laminate capable of obtaining a cured sealant with a flat surface and a cured resin layer that suppresses deformation. Preferably it is 0.1-500 mass parts, More preferably, it is 1-200 mass parts.

The hardening accelerator (B3) is a compound having a function of increasing the thermosetting speed when thermosetting the formed thermosetting resin layer. Hardening accelerators (B3), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl) phenol; 2- Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles such as imidazole; tributylphosphine (phosphine), diphenylphosphine, triphenylphosphine and other organic phosphines; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenyl Tetraphenylboron salts such as phenyl borate and the like. These curing accelerators (B3) may be used alone or in combination of two or more.

The content of the hardening accelerator (B3) is relative to the content of the epoxy compound (B1) and the thermosetting agent (B2) from the viewpoint of a warpage-resistant laminate capable of obtaining a hardened sealing body that suppresses deformation and has a flat surface. The total amount is 100 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, particularly preferably 0.3 to 4 parts by mass.

(colorant (C)) The thermosetting resin composition used in one aspect of the present invention may further have a colorant (C). The thermosetting resin layer formed from the thermosetting resin composition containing the coloring agent (C), when thermosetting as the cured resin layer, not only imparts the effect of easily judging whether the cured resin layer is pasted from the appearance In addition, it also has the effect of shielding infrared rays generated by surrounding devices and preventing malfunction of sealing objects (semiconductor chips, etc.).

As the colorant (C), organic or inorganic pigments and dyes can be used. As the dye, for example, any of acid dyes, reactive dyes, direct dyes, disperse dyes, and cationic dyes can be used. In addition, the content of the pigment is not particularly limited, and it can be appropriately selected from known pigments and used. Among these, black pigments are preferable from the viewpoint of having good shielding properties against electromagnetic waves or infrared rays. Black pigments include, for example, carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, etc., and carbon black is preferable from the viewpoint of improving the reliability of semiconductor wafers. Moreover, these coloring agents (C) may be used individually or in combination of 2 or more types.

Among them, in the thermosetting resin composition used in one aspect of the present invention, the content of the colorant (C) is less than 8% with respect to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition. Mass% is preferred. When the content of the coloring agent (C) is less than 8% by mass, the presence or absence of cracks or chips on the wafer surface can be visually confirmed as a warpage-resistant laminate. Based on the above viewpoint, in the thermosetting resin composition used in one aspect of the present invention, the content of the colorant (C) is preferably preferably It is less than 5% by mass, more preferably less than 2% by mass, most preferably less than 1% by mass, most preferably less than 0.5% by mass. In addition, from the viewpoint that the cured resin layer obtained by thermosetting the formed thermosetting resin layer can produce effects such as shielding infrared rays, the content of the colorant (C) relative to the active ingredient of the thermosetting resin composition The total amount (100% by mass) is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, particularly preferably at least 0.10% by mass, most preferably at least 0.15% by mass.

(couplant (D)) The thermosetting resin composition used in one aspect of the present invention may further contain a coupling agent (D). Using the thermosetting resin layer formed from the thermosetting resin composition containing the coupling agent (D) can improve the adhesiveness with the sealing object when placing the object to be sealed. In addition, the cured resin layer obtained by thermosetting the thermosetting resin layer can improve water resistance without impairing heat resistance.

The coupling agent (D) is preferably a compound capable of reacting with the functional group of the component (A) or component (B), specifically, a silane coupling agent is preferred. Silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-(methacryloxypropyl)trimethoxysilane, 3-aminopropyltrimethoxysilane, N-6-(aminoethyl)-3-amine propyltrimethoxysilane, N-6-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- Ureide (ureide) propyl triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl dimethoxysilane, bis(3-triethoxysilylpropane) base) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetyloxysilane, imidazole silane, etc. These coupling agents (D) may be used alone or in combination of two or more.

The molecular weight of coupling agent (D) is preferably 100-15,000, more preferably 125-10,000, more preferably 150-5,000, particularly preferably 1,75-3,000, most preferably 200-2,000.

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

(Inorganic Filler (E)) The thermosetting resin composition used in one aspect of the present invention further contains an inorganic filler (E) from the viewpoint of being a warpage-resistant laminate capable of producing a cured sealing body that suppresses deformation and has a flat surface. good. When using a thermosetting resin layer formed of a thermosetting resin composition containing an inorganic filler (E), when the sealing material is thermally cured, the contraction stress between the two surfaces of the cured sealing body can be reduced. The degree of thermosetting of the thermosetting resin layer can be adjusted. The result will be a hardened seal that resists deformation and has a flat surface. In addition, by adjusting the thermal expansion coefficient of the cured resin layer obtained by thermosetting the formed thermosetting resin layer to an appropriate range, the reliability of the object to be sealed can be improved. In addition, the moisture absorption rate of the cured resin layer can be reduced.

Inorganic fillers (E), for example, powders of silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride, etc., spheroidized particles, single crystal fibers And non-thermally expandable particles such as glass fibers. These inorganic fillers (E) may be used alone or in combination of two or more. Among them, silicon dioxide or alumina is preferable as a warpage-resistant laminate capable of producing a cured sealing body that suppresses deformation and has a flat surface.

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

The content of the component (E) is relative to the total amount (100% by mass) of the active ingredients of the thermosetting resin composition from the viewpoint of a warpage-resistant laminate capable of obtaining a hardened sealing body that suppresses deformation and has a flat surface , preferably 25-80% by mass, more preferably 30-70% by mass, particularly preferably 40-65% by mass, most preferably 45-60% by mass.

(other additives) The thermosetting resin composition used in one aspect of the present invention may further contain other additives other than the above-mentioned components (A) to (E) within the range that does not impair the effect of the present invention. Other additives, such as cross-linking agents, leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, absorbers, chain transfer agents, etc. Among them, the total content of other additives other than components (A) to (E) is preferably 0 to 20% by mass, more preferably It is 0 to 10% by mass, particularly preferably 0 to 5% by mass.

Curable resin layer (I), as shown in Fig. 1, Fig. 2, Fig. 3, when only consisting of a single layer of thermosetting resin layer (X1), the thermosetting resin layer of this single layer (X1) ) has the above constitutional content. The hardening resin layer (I), as shown in FIG. 4, includes the first thermosetting resin layer (X1-1) on the side of the support layer (II), and the side opposite to the support layer (II) ( As shown in the case of the second thermosetting resin layer (X1-2) on the first surface side), when there are two or more thermosetting resin layers (X1), the above two or more layers of the thermosetting resin The minimum value (T _1a ) of the aforementioned minimum hardening temperature (T ₁ ) in the layer (X1), whichever is lower than the foaming initiation temperature (T ₂ ) of the heat-expandable particles contained in the support layer (II), is good. If the minimum curing temperature (T ₁ ) of the plural layers contained in the thermosetting resin layer (X1) is different, the curable resin layer showing these minimum values (T _1a ) has higher thermal expansion The foaming initiation temperature (T ₂ ) of the particles is the lower minimum hardening temperature (T ₁ ), so when the hardening resin layer hardens, the expansion of the heat-expandable particles can be suppressed, and the formation of the heat-expandable particles with the hardening resin layer can be prevented. Excessively tight. Among the plural layers constituting the thermosetting resin layer (X1), the effect of the layer having T _1a is more pronounced when it is arranged on the side closest to the support layer, even if the other layers among the above plural layers are (T _1a ), the detachability between the cured resin layer (I') and the support layer (II) is not easily impaired. One of the reasons is that the other layers are hardened while the expansion of the heat-expandable particles is suppressed, so when the heat-expandable particles are expanded subsequently, the peelability is improved due to the presence of the other layers after hardening.

Moreover, the 1st thermosetting resin layer (X1-1) and the 2nd thermosetting resin layer (X1-2), for example, may mutually differ from each other in adhesive force. In this case, the second thermosetting resin layer (X1-2) located on the first surface side has a surface adhesive force that is higher than that of the second thermosetting resin layer (X1-1) compared to the first thermosetting resin layer (X1-1). The one with higher permanent resin layer (X1-2) is better. Also, to make the adhesion of the second thermosetting resin layer higher than that of the first thermosetting resin layer, for example, select one that can produce high adhesion due to changing the type of coupling agent, or reduce the inorganic Addition ratio of filling materials, etc. Also, the shear force of the first thermosetting resin layer (X1-1) and the shear force of the second thermosetting resin layer (X1-2) can be different, for example, the shear force of the former can be increased. . In this case, for example, the amount of the inorganic filler added to the first thermosetting resin layer (X1-1) can be increased to make the shearing force stronger than that of the second thermosetting resin layer (X1-2). big.

(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 the first layer on the support layer side and the second layer on the first surface side, and the first layer is the thermosetting resin layer (X1-1) , the second layer is preferably an energy ray curable resin layer (X2). The thermosetting resin layer (X1-1) has the above-mentioned constitutional content. The energy ray curable resin layer (X2) is preferably formed of an energy ray curable adhesive composition containing an energy ray curable adhesive resin and a photopolymerization initiator. Compared with the thermosetting resin layer, the energy ray curable resin layer (X2) can be easily adjusted to increase the adhesive force, so it is easy to securely fix the object to be sealed on the first surface. When the energy ray-curable resin layer using these energy ray-curable adhesive compositions is irradiated with energy rays to be cured, it is possible to prevent the curable resin layer from shrinking due to curing when the sealing material is thermally cured as described later. It is beneficial to prevent the phenomenon of warping of the hardened sealing body. In addition, compared with the thermosetting adhesive composition, when heated at a high temperature, softening occurs mainly in the initial stage of curing, which may cause wafer shifting. The energy ray-curing adhesive composition of the present invention , Even when hardened by irradiation of energy rays, no softening occurs, so the phenomenon of wafer offset accompanying the hardening process can be avoided. Also, the energy rays include, for example, ultraviolet rays, electron rays, radiation rays, etc., and ultraviolet rays are preferable from the viewpoint of the ease of obtaining the curable resin composition and the ease of handling of the energy ray irradiation device.

The energy ray-curable adhesive composition may be an energy ray-curable adhesive resin obtained by introducing polymerizable functional groups such as (meth)acryl groups and vinyl groups into the side chains of the above-mentioned adhesive resins. A composition, or a composition containing a monomer or oligomer having a polymerizable functional group may be used. Moreover, in these compositions, it is preferable to further contain a photopolymerization initiator.

Photopolymerization initiators, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethyl Thiuram monosulfide, azobisisobutyronitrile, dibenzyl ester, diacetyl ester, 8-chloroanthraquinone, etc. These photopolymerization initiators may be used alone, or may be used in combination of 2 or more types. The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 parts by mass relative to 100 parts by mass of the energy ray-curable adhesive resin or 100 parts by mass of a monomer or oligomer having a polymerizable functional group ~5 parts by mass, particularly preferably 0.05 to 3 parts by mass, most preferably 0.1 to 3 parts by mass.

It is also possible to increase the shear force of the curable resin layer (I) as a whole by making the shear force of the thermosetting resin layer (X1-1) greater than the shear force of the energy ray curable resin layer (X2). .

＜Support layer (II)＞ The support layer (II) which the laminated body of one aspect of this invention has has a base material (Y) and an adhesive agent layer (V), and at least one of the base material (Y) and the adhesive agent layer (V) is Those containing heat-expandable particles are preferable. As described above, the support layer (II) is a layer separated from the curable resin layer (I) by expansion treatment or the like, and has a function as a temporary fixing layer. When the layer containing heat-expandable particles is included in the composition of the substrate (Y) and the composition of the adhesive layer (V), the support layer (II) used in one aspect of the present invention ), which are divided into the following forms. ・The first aspect of the support layer (II): The support layer (II) provided with the base material (Y) which has the expandable base material layer (Y1) containing a heat-expandable particle. ・The second aspect of the support layer (II): On one side of the base material (Y), a second adhesive layer (V2) of an expandable adhesive layer containing heat-expandable particles is provided, and on the other side On the surface, there is a supporting layer (II) of the first adhesive layer (V1) having a non-expandable adhesive layer.

(the first aspect of the supporting layer (II)) In the first aspect of the support layer (II), as shown in Figs. 1-2, 4, and 5, the substrate (Y) has an expandable substrate layer (Y1) containing heat-expandable particles. The interface P is preferably a non-swellable adhesive layer from the viewpoint that the whole can be easily separated with a little force. Specifically, in the support layer (II) of the laminated body 1a, 1b shown in Figure 1, the laminated body 4 shown in Figure 4, and the laminated body 5 shown in Figure 5, the adhesive layer (V1) A non-expandable adhesive layer is preferred. Moreover, in the support layer (II) which the laminated body 2a, 2b shown in FIG. The adhesive layer is better. Like the first aspect of the support layer (II), since the base material (Y) has an expandable base material layer (Y1), the adhesive layer (V1) does not necessarily have expandability, and does not need to be subjected to a composition imparting expandability. , Composition and manufacturing process, etc. are constrained. In this way, when designing the adhesive layer (V1), for example, performance such as adhesiveness, productivity, economical efficiency, etc., can be designed with priority for expected performance other than expansion, and the adhesive layer (V) can be improved. design freedom.

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

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

Also, in this specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of adhesive layers, the above-mentioned "thickness of the adhesive layer (V)" refers to the thickness of each adhesive layer. (In FIG. 2, it means the respective thickness of the 1st adhesive layer (V1-1) and the 2nd adhesive layer (V1-2)). In addition, in this specification, the thickness of each layer which comprises a laminate means the value measured by the method described in an Example.

In the first aspect of the support layer (II), the thickness ratio [(Y1)/(V)] of the expandable base material layer (Y1) before the expansion treatment to the adhesive layer (V) is preferably 1,000 or less , more preferably below 200, particularly preferably below 60, most preferably below 30. When the thickness ratio is 1,000 or less, a laminate can be easily separated as a whole at the interface P between the support layer (II) and the cured resin layer (I') after expansion treatment with a little force. . Also, the thickness ratio is preferably at least 0.2, more preferably at least 0.5, particularly preferably at least 1.0, most preferably at least 5.0.

Also, in the first aspect of the support layer (II), the base material (Y), as shown in Figure 1(a), may be composed only of the expandable base material layer (Y1), or As shown in (b), it has an expandable base material layer (Y1) on the curable resin layer (I) side, and has a non-expandable base material layer (Y2) on the adhesive layer (V) side.

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

(the second aspect of the supporting layer (II)) The second aspect of the support layer (II), as shown in Figure 3, for example, on the surface of one side of the substrate (Y), a first adhesive layer (V1) of a non-expandable adhesive layer is arranged, The second adhesive layer (V2) of the expandable adhesive layer containing heat-expandable particles is disposed on the other surface. Also, in the second aspect of the support layer (II), the second adhesive layer (V2) of the expandable adhesive layer is in direct contact with the curable resin layer (I). In the second aspect of the support layer (II), the substrate (Y) is preferably a non-expandable substrate. The non-expandable base material is preferably composed of only the non-expandable base material layer (Y2).

In the second aspect of the support layer (II), the thickness of the second adhesive layer (V2) of the intumescent adhesive layer before the expansion treatment, and the first adhesive layer (V1) of the non-expandable adhesive layer The ratio [(V2)/(V1)] is preferably 0.1-80, more preferably 0.3-50, particularly preferably 0.5-15.

Also, in the second aspect of the support layer (II), the thickness ratio of the second adhesive layer (V2) of the expandable adhesive layer before the expansion treatment to the substrate (Y) [(V2)/(Y )], preferably 0.05-20, more preferably 0.1-10, particularly preferably 0.2-3. In the second aspect of the support layer (II), the thickness of the support layer (II) is preferably 0.05-20 μm, more preferably 0.1-10 μm, particularly preferably 0.2-3 μm.

Hereinafter, while describing the thermally expandable particles contained in any layer constituting the support layer (II), the expandable base material layer (Y1) and the non-expandable base material layer ( Y2), and the adhesive layer (V).

(Heat-expandable particles) The expandable particles used in one aspect of the present invention, as long as they are heated, the body expands to form unevenness on the adhesive surface of the adhesive layer (V2), thereby reducing the adhesive force with the adherend. There are no special restrictions on those times. The heat-expandable particles have better versatility and handling properties than energy-line-expandable particles expanded by irradiation with energy rays. The heat-expandable particles used in one aspect of the present invention have an average particle diameter before expansion at 23°C, preferably 3 to 100 μm, more preferably 4 to 70 μm, particularly preferably 6 to 60 μm, most preferably 10 ~50 μm. Also, the average particle diameter before expansion of the heat-expandable particles refers to the volume median particle diameter (D ₅₀ ), which is measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern Corporation, product name "MASTERSIZER 3000") In the particle distribution of the heat-expandable particles before expansion, the cumulative volume frequency calculated from the smaller particle diameter side of the heat-expandable particles before expansion corresponds to the particle diameter at 50%.

The heat-expandable particles used in one aspect of the present invention have a 90% particle size (D ₉₀ ) before expansion at 23°C, preferably 10-150 μm, more preferably 20-100 μm, and most preferably 25-90 μm , the optimum is 30-80 μm. In addition, the 90% particle size (D ₉₀ ) of thermally expandable particles before expansion refers to the thermal expansion before expansion measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern, product name "MASTERSIZER 3000") In the particle distribution of thermally expandable particles, it means the particle size at which the cumulative volume frequency reaches 90% when calculated from the smaller particle size side of the heat-expandable particles before expansion.

The heat-expandable particles used in one aspect of the present invention are those that do not expand when the sealing material is hardened, and have a higher expansion initiation temperature (t) than the hardening temperature of the sealing material. Specifically, heat-expandable particles adjusted to an expansion initiation temperature (t) of 60 to 270°C are preferable. Also, the expansion initiation temperature (t) can be appropriately selected in accordance with the hardening temperature of the sealing material used. In addition, in this specification, the expansion start temperature (t) of a heat-expandable particle means the value measured by the method described in an Example.

The heat-expandable particles are preferably composed of a shell made of thermoplastic resin and a microencapsulated blowing agent that is wrapped in the shell and contains an inner component that will be vaporized when heated to a specific temperature. Thermoplastic resins that form the shell of microencapsulated blowing agents, such as vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polychlorinated Vinylene, Polyethylene, etc.

Included components contained in the shell, for example, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, isoheptane, Isooctane, Isononane, Isodecane, Cyclopropane, Cyclobutane, Cyclopentane, Cyclohexane, Cycloheptane, Cyclooctane, Neopentane, Dodecane, Isododecane, Cyclodecane Tridecane, Hexylcyclohexane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Heptadecane, Octadecane, Nonadecane, Isotridecane, 4-Methyldodecane, Isotridecane Tetradecane, Isopentadecane, Isohexadecane, 2,2,4,4,6,8,8-Heptamethylnonane, Isoheptadecane, Isooctadecane, Isnonadecane, 2 ,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane, Pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. These contained components may be used alone or in combination of two or more. The expansion initiation temperature (t) of the heat-expandable particles can be adjusted by properly selecting the type of inner package components. Generally, it is better to adjust it to be higher than the minimum hardening temperature _T1 of the curable resin layer (I).

The thermally expandable particles used in one aspect of the present invention have a maximum volume expansion rate of preferably 1.5 to 100 times, more preferably 2 to 80 times, especially when heated to a temperature above the expansion initiation temperature (t). The best is 2.5 to 60 times, and the best is 3 to 40 times.

＜Expandable Base Layer (Y1)＞ The expandable base material layer (Y1) included in the support layer (II) used in one aspect of the present invention contains heat-expandable particles and is a layer formed by undergoing a specific thermal expansion treatment to form an expanded layer.

Also, from the viewpoint of improving the interlayer adhesion between the expandable base material layer (Y1) and other laminated layers, the surface of the expandable base material layer (Y1) can be oxidized, roughened, etc. Surface treatment, easy-to-adhesive treatment, or primer treatment. Oxidation methods, such as corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment, etc., roughening methods, such as sandblasting, solvent treatment, etc.

In one aspect of the present invention, it is preferable that the expandable base material layer (Y1) satisfies the following requirement (1).・Requirement (1): The storage elastic modulus E'(t) of the expandable base material layer (Y1) at the expansion initiation temperature (t) of the thermally expandable particles is 1.0×10 ⁷ Pa or less. In addition, in this specification, the storage elastic modulus E' of the expandable base material layer (Y1) at a specific temperature means the value measured by the method described in an Example.

The above requirement (1) is also referred to as an index indicating the rigidity of the thermally expandable particle before expansion of the expandable base material layer (Y1). From the point of view that the interface P between the support layer (II) and the cured resin layer (I') can be easily separated with only a little force, when heated to a temperature above the expansion initiation temperature (t), the support layer ( II) The surface on the side to be laminated with the curable resin layer (I) needs to be easily uneven. That is, the expandable base material layer (Y1) that satisfies the above-mentioned requirement (1) can expand the thermally expandable particles to a greater extent at the expansion initiation temperature (t), and can be formed on the curable resin layer (I) layer. On the surface of the support layer (II) on the side where it is combined, unevenness is more likely to be formed. As a result, a laminate can be obtained that can be easily separated at the interface P between the support layer (II) and the cured resin layer (I') with only a little force.

The storage elastic modulus E'(t) of the expandable base material layer (Y1) stipulated in the requirement (1) is preferably 9.0×10 ⁶ Pa or less, more preferably 8.0×10 ⁶ Pa or less, especially from the above viewpoint. Preferably, it is 6.0×10 ⁶ Pa or less, most preferably, it is 4.0×10 ⁶ Pa or less. In addition, in order to suppress the flow of the thermally expandable particles after expansion and improve the shape retention of the unevenness formed on the surface of the support layer (II) laminated on the side of the curable resin layer (I), only From the viewpoint of easy separation with a little force, the storage elastic modulus E'(t) of the expandable base material layer (Y1) specified in the requirement (1) is preferably 1.0×10 ³ Pa or more, more preferably 1.0×10 ⁴ Pa or more, particularly preferably 1.0×10 ⁵ Pa or more.

The expandable base material 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 if necessary within the range not impairing the effect of the present invention. Additives for substrates, such as UV absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiadhesive agents, colorants, etc. Moreover, these additives for base materials may be used individually, respectively, and may be used in combination of 2 or more types. When these base material additives are contained, the content of each base material additive is preferably from 0.0001 to 20 parts by mass, more preferably from 0.001 to 10 parts by mass, based on 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 base material layer (Y1) or the total amount (100% by mass) of active ingredients of the resin composition (y) , more preferably 5 to 35% by mass, particularly preferably 10 to 30% by mass, most preferably 15 to 25% by mass.

The resin containing the resin composition (y) as a material for forming the expandable base layer (Y1) may be a non-adhesive resin or an adhesive resin. That is, when the resin contained in the resin composition (y) is an adhesive resin, in the process of forming the expandable base material layer (Y1) from the resin composition (y), the adhesive resin may interact with the polymerizable compound. Since the polymerization reaction is carried out to make the obtained resin a non-adhesive resin, it is only necessary that the expandable base material layer (Y1) containing the resin is non-adhesive.

The mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably from 1,000 to 1,000,000, more preferably from 1,000 to 700,000, and most preferably from 1,000 to 500,000. Also, when the resin is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and may be one of block copolymers, random copolymers, and graft copolymers. either.

The content of the above-mentioned 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 active ingredients of the resin composition (y), More preferably, it is 60-95 mass %, Most preferably, it is 65-90 mass %, Most preferably, it is 70-85 mass %.

Also, from the viewpoint of forming the expandable base material layer (Y1) that satisfies the above-mentioned requirement (1), the above-mentioned resin contained in the resin composition (y) may be composed of a urethane-based resin and an olefin-based resin. One or more selected ones are preferred. In addition, the above-mentioned urethane acrylate resin is a urethane acrylate resin obtained by polymerizing a urethane prepolymer (UP) and a vinyl compound containing (meth)acrylate ) is preferred.

(Urethane acrylate resin (U1)) The urethane prepolymer (UP) which is the main chain of the urethane-based resin (U1) is, for example, a reaction product of a polyalcohol and a polyvalent isocyanate. Also, the urethane prepolymer (UP) is preferably obtained by subjecting it to a chain extension reaction using a chain extender.

Polyalcohols used as raw materials for urethane prepolymers (UP), such as alkylene-type polyols, ether-type polyols, ester-type polyols, amide ester-type polyols, and ester-ether-type polyols , Carbonate polyalcohol, etc. These polyalcohols may be used alone, or may be used in combination of 2 or more types. The polyalcohols used in one aspect of the present invention are preferably diols, preferably ester diols, alkylene diols and carbonate diols, and ester diols and carbonate diols. Alcohol is better.

Ester diols, for example, chains consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. Alkanediol; Alkanediol such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; etc., one or more selected from diols, combined with phthalic acid, isophthalic acid, terephthalic acid Phthalic acid, naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chlorine Bacteric acid, maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid Dicarboxylic acids such as formic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid, and polycondensates of one or more selected from these anhydrous substances. Specifically, for example, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol , polyneopentyl adipate diol, polyvinyl propylene adipate diol, polyethylene butyl adipate diol, polybutylene hexamethyl adipate diol, Polydiethylene adipate diol, poly(tetramethylene ether) adipate diol, poly(3-methylpentene adipate) diol, polyvinyl acetate diol , polyethylene sebacate diol, polybutylene azelate diol, polybutene sebacate diol and polyneopentyl terephthalate diol, etc.

Alkylene diols, for example, of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. Alkanediols; Alkanediols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; Polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutene glycol; Polybutene glycol, etc. polyoxyalkylene glycol; etc.

Carbonate diols, for example, 1,4-tetramethylcarbonate diol, 1,5-pentamethylcarbonate diol, 1,6-hexylene carbonate diol, 1,2 -Propylene carbonate diol, 1,3-propylene carbonate diol, 2,2-dimethyl propylene carbonate diol, 1,7-heptyl propylene carbonate diol, 1 , 8-octyl methylene carbonate diol, 1,4-cyclohexane carbonate diol, etc.

As polyvalent isocyanate which is a raw material of a urethane prepolymer (UP), aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned, for example. These polyvalent isocyanates may be used alone or in combination of two or more. In addition, these polyvalent isocyanates may also be trimethylolpropane adduct-type modified products, biuret-type modified products reacted with water, and isocyanurates containing isocyanurate rings. type transgender.

Among these, the polyvalent isocyanate used in one aspect of the present invention is preferably a diisocyanate, such as 4,4'-diphenylmethane diisocyanate (MDI), 2,4-cresyl diisocyanate One or more selected from isocyanate (2,4-TDI), 2,6-cresyl diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), and alicyclic diisocyanate better.

Cycloaliphatic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3 -Cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc., and isophorone Diisocyanate (IPDI) is preferred.

In one aspect of the present invention, the urethane prepolymer (UP) as the main chain of the urethane acrylate resin (U1) is a reaction product of a diol and a diisocyanate, and has Ethylenically unsaturated linear urethane prepolymers are preferred. A method of introducing ethylenically unsaturated groups at both ends of the linear urethane prepolymer, for example, a linear urethane prepolymer obtained by reacting a diol with a diisocyanate compound The NCO group at the end of the compound, the method of reacting with hydroxyalkyl (meth)acrylate, etc.

Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxy(meth)propylacrylate, 3-hydroxy(meth)acrylate, 2-hydroxy(methyl)acrylate ) butyl acrylate, 3-hydroxy(meth)acrylate, 4-hydroxy(meth)acrylate, etc.

The vinyl compound which is a side chain of the urethane-based resin (U1) contains at least (meth)acrylate. (Meth)acrylates are preferably one or more selected from alkyl (meth)acrylates and hydroxyalkyl (meth)acrylates, and alkyl (meth)acrylates and hydroxy (meth)acrylates are used in combination. Alkyl esters are preferred.

When an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate are used together, the addition ratio of the hydroxyalkyl (meth)acrylate is preferably 0.1 to 100 parts by mass of the alkyl (meth)acrylate. 100 parts by mass, more preferably 0.5-30 parts by mass, particularly preferably 1.0-20 parts by mass, most preferably 1.5-10 parts by mass.

The carbon number of the alkyl group which this alkyl (meth)acrylate has is preferably 1-24, More preferably, it is 1-12, Especially preferably, it is 1-8, Most preferably, it is 1-3.

Also, the hydroxyalkyl (meth)acrylate is, for example, the same as the hydroxyalkyl (meth)acrylate used when introducing an ethylenically unsaturated group to both ends of the linear urethane prepolymer. the content.

Vinyl compounds other than (meth)acrylates, such as aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether Vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, meth(acrylamide) etc. Monomers containing polar groups; etc. These may be used alone, or may be used in combination of 2 or more types.

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

In the vinyl compound, the total content of the alkyl (meth)acrylate and the hydroxyalkyl (meth)acrylate is preferably from 40 to 100% by mass, more preferably It is 65 to 100% by mass, particularly preferably 80 to 100% by mass, most preferably 90 to 100% by mass.

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

(Olefin resin) Among the resins contained in the resin composition (y), preferable olefin-based resins are, for example, polymers having at least structural units derived from olefin monomers. The above-mentioned olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, specifically, vinyl, propenyl, butenyl, isobutenyl, 1-hexenyl, and the like. Among these, vinyl and acryl groups are preferable.

Specifically, olefin-based resins such as ultra-low-density polyethylene (VLDPE, density: 880 kg/m ³ or more and less than 910 kg/m ³ ), low-density polyethylene (LDPE, density: 910 kg/m ³ or more, up to 915kg/m ³ ), medium density polyethylene (MDPE, density: above 915kg/m ³ , less than 942kg/m ³ ), high density polyethylene (HDPE, density: above 942kg/m ³ ), linear low Polyethylene resin such as density polyethylene; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin-based elastomer (TPO); poly(4-methyl-1-pentene) (PMP); Ethylene-vinyl acetate copolymer (EVA); Ethylene-vinyl alcohol copolymer (EVOH); Olefin-based terpolymers such as ethylene-propylene-(5-ethylidene-2-norcamphene); wait.

In one aspect of the present invention, the olefin resin may be denatured by one or more denaturations selected from acid denaturation, hydroxyl denaturation, and acrylic denaturation.

For example, acid-modified olefin-based resins obtained by acid-modifying olefin-based resins, such as denatured polymers obtained by graft polymerization of the above-mentioned non-denatured olefin-based resins with unsaturated carboxylic acids or their anhydrides, etc. . The above-mentioned unsaturated carboxylic acids or their anhydrides, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic acid, Toic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norcamphene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc. Moreover, an unsaturated carboxylic acid or its anhydride may be used individually or in combination of 2 or more types.

An acrylic-modified olefin-based resin obtained by subjecting an olefin-based resin to denaturation with an acrylic group, for example, on the above-mentioned non-denatured olefin-based resin as a main chain, as a side chain, undergoes a reaction with an alkyl (meth)acrylate Denatured polymers obtained by graft polymerization, etc. The carbon number of the alkyl group which the said alkyl (meth)acrylate has is preferably 1-20, More preferably, it is 1-16, Most preferably, it is 1-12. The aforementioned alkyl (meth)acrylate is, for example, the same as the compound that can be selected as the monomer (a1') described later.

The hydroxy-denatured olefin-based resin obtained by modifying the hydroxyl group of an olefin-based resin is, for example, a denatured polymer obtained by graft-polymerizing the above-mentioned non-denatured olefin-based resin as a main chain with a compound containing a hydroxyl group. The compounds containing hydroxyl groups mentioned above, for example, 2-hydroxy (meth) acrylate, 2-hydroxy (meth) acrylate, 3-hydroxy (meth) acrylate, 2-hydroxy (meth) acrylate Hydroxyalkyl (meth)acrylates such as esters, 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol, etc.

(Resins other than urethane-based resins and olefin-based resins) In one aspect of the present invention, the resin composition (y) may contain resins other than urethane-based resins and olefin-based resins within a range that does not impair the effects of the present invention. These resins, for example, vinyl resins such as polyvinyl dichloride, polyvinylidene chloride, and polyvinyl alcohol; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthyl ester, etc. Polyester resins; Polystyrene; Acrylonitrile-butadiene-styrene copolymer; Cellulose triacetate; Polycarbonate; Polyurethanes not equivalent to urethane acrylate resins; Polyurethane ; Polyether-ether ketone; polyether ketone; polyphenylene sulfide;

Here, from the viewpoint of forming the expandable base material layer (Y1) satisfying the above-mentioned requirement (1), the content ratio of the resin other than the urethane-based resin and the olefin-based resin in the resin composition (y) is given by Less is better. The content ratio of resins other than urethane-based resins and olefin-based resins is preferably less than 30 parts by mass, more preferably not more than 100 parts by mass of the total amount of resins contained in the resin composition (y). 20 parts by mass, more preferably less than 10 parts by mass, particularly preferably less than 5 parts by mass, most preferably less than 1 part by mass.

(Solvent-free resin composition (y1)) The resin composition (y) used in one aspect of the present invention is composed of an oligomer having an ethylenically unsaturated group with a mass average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer, and the aforementioned thermal expansion Non-solvent type resin composition (y1) which is composed of non-toxic particles and no solvent is added. In the solvent-free resin composition (y1), since no solvent is added, the energy ray polymerizable monomer is one that can improve the plasticity of the above-mentioned oligomer. When the coating film formed of the solvent-free resin composition (y1) is irradiated with energy rays, it is easy to form an expandable base material layer (Y1) satisfying the above requirement (1). In addition, the kind, shape, and addition amount (content) of the heat-expandable particle added to the non-solvent type resin composition (y1) are as above-mentioned.

The mass average molecular weight (Mw) of the oligomer contained in the solvent-free resin composition (y1) is 50,000 or less, preferably 1,000 to 50,000, more preferably 20,00 to 40,000, most preferably 3,000 to 35,000, The best range is 4,000 to 30,000.

In addition, the above-mentioned oligomer may be any one having an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less among the resins contained in the above-mentioned resin composition (y). Polymer (UP) is preferred. Moreover, the denatured olefin resin which has an ethylenically unsaturated group can also be used for this oligomer.

In the solvent-free resin composition (y1), the total content of the above-mentioned oligomers and energy ray polymerizable monomers is preferably from 50 to 99% by mass, more preferably 60 to 95% by mass, particularly preferably 65 to 90% by mass, most preferably 70 to 85% by mass.

Energy ray polymerizable monomers such as isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate Cyclohexyl (meth)acrylate, alicyclic polymerizable compounds such as cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl acrylate, etc.; phenyl hydroxypropyl acrylate, benzyl acrylate, phenol oxirane Aromatic polymeric compounds such as denatured acrylates; heterocyclic polymeric compounds such as tetrahydrofurfuryl (meth)acrylate, morpholinyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, etc. wait. These energy ray polymerizable monomers may be used alone or in combination of two or more.

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

In one aspect of the present invention, it is preferable to add a photopolymerization initiator to the solvent-free resin composition (y1). When a photopolymerization initiator is contained, the curing reaction can sufficiently proceed even when irradiated with energy rays of relatively low energy.

Photopolymerization initiators, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethyl Thiuram monosulfide, azobisisobutyronitrile, dibenzyl ester, diacetyl ester, 8-chloroanthraquinone, etc. These photopolymerization initiators may be used alone, or may be used in combination of 2 or more types.

The amount of the photopolymerization initiator to be added is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, and most preferably It is 0.02 to 3 parts by mass.

<Non-expandable base material layer (Y2)> The forming material of the non-expandable base material layer (Y2) constituting the base material (Y), for example, paper, resin, metal, etc., can be combined with one aspect of the present invention. Make appropriate choices for the use of the laminated body. Among them, in one aspect of the present invention, when the thermally expandable particles contained in the expandable base material layer (Y1) are expanded, the non-expandable base material layer (Y2) side of the expandable base material layer (Y1) can be suppressed The surface of the non-expandable base material layer (Y2) has unevenness even if subjected to thermal expansion. It is better to have rigidity that does not cause deformation due to the expansion of non-volatile particles. Specifically, the storage elastic modulus E'(t) of the non-expandable base material layer (Y2) at the temperature (t) at which the thermally expandable particles start to expand is preferably 1.1×10 ⁷ Pa or more.

Paper materials, such as thin leaf paper, medium paper, high quality paper, impregnated paper, coated paper, drawing paper, sulfuric acid paper, cellophane, etc. Resins, for example, polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl dichloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc.; Polyester-based resins such as ethylene terephthalate, polybutylene terephthalate, and polyethylene naphthyl ester; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; Polycarbonate; Urethane resins such as polyurethane, acrylic denatured polyurethane, etc.; Polymethylpentene; Polyethylene; Polyether-etherketone; Sulfide; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resins; acrylic resins; fluorine-based resins, etc. Metals such as aluminum, tin, chromium, titanium, etc.

These formation materials may consist of 1 type, and may be used in combination of 2 or more types. The non-expandable base material layer (Y2) used in combination of two or more forming materials is, for example, paper laminated with a thermoplastic resin such as polyethylene, or a metal film formed on the surface of a resin film or sheet containing a resin. In addition, the method of forming the metal layer is, for example, a method of vapor-depositing the above-mentioned metals using a PVD method such as vacuum evaporation, sputtering, or ion plating, or attaching a metal foil formed of the above-mentioned metals using a general adhesive. method etc.

Also, from the viewpoint of improving interlayer adhesion between other layers laminated with the non-expandable base material layer (Y2), when the non-expandable base material layer (Y2) contains a resin, the non-expandable base material layer (Y2) can be The surface of (Y2) is subjected to surface treatment, easy-adhesive treatment, or primer treatment by oxidation, embossing, or the like in the same manner as the above-mentioned expandable base material layer (Y1).

In addition, when the non-expandable base material layer (Y2) contains a resin, it may contain the resin composition (y) or the above-mentioned additives for the base material together with the resin.

The non-expandable base material layer (Y2) is a non-expandable layer judged based on the above method. Therefore, the volume change rate (%) of the non-expandable base material layer (Y2) calculated from the above formula is less than 5% by volume, preferably less than 2% by volume, more preferably less than 1% by volume, Most preferably, it is less than 0.1% by volume, and most preferably, it is less than 0.01% by volume.

Moreover, in the non-expandable base material layer (Y2), when the volume change rate is in the said range, thermally expandable particle|grains may be contained. For example, by selecting the resin contained in the non-expandable base material layer (Y2), even when thermally expandable particles are contained, the volume change rate can be adjusted to the above range. Among these, it is preferable that the non-expandable base material layer (Y2) does not contain thermally expandable particles. When the non-expandable base material layer (Y2) contains heat-expandable particles, the less the content, the better, specifically, the content of heat-expandable particles, relative to the total mass of the non-expandable base material layer (Y2) (100 mass %), usually less than 3 mass%, preferably less than 1 mass%, more preferably less than 0.1 mass%, particularly preferably less than 0.01 mass%, most preferably less than 0.001 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 of the adhesive composition (v) containing an adhesive resin. In addition, the adhesive composition (v) may contain adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary. Hereinafter, each component contained in the adhesive composition (v) will be described. In addition, the support layer (II), regardless of having the first adhesive layer (V1-1) or (V1), and the second adhesive layer (V1-2) or (V2), or having the first adhesive layer In the case of (V1-1) or (V1), and the second adhesive layer (V1-2) or (V2), both can be formed from the adhesive composition (v) containing the following components.

(adhesive resin) The adhesive resin used in one aspect of the present invention is preferably a polymer having adhesiveness alone and having a mass average molecular weight (Mw) of 10,000 or more. The mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 1.5 million, and most preferably 3 from the viewpoint of improving the adhesive force. Ten thousand to one million.

Specific adhesive resins, for example, 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 wait. These adhesive resins may be used alone, or may be used in combination of 2 or more types. Also, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, and may be block copolymers, random copolymers, or grafted copolymers. any of the copolymers.

In one aspect of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of producing excellent adhesive force. Also, in the case of using the support layer (II) having the first adhesive layer (V1-1) or (V1), and the second adhesive layer (V1-2) or (V2), the curable resin layer ( I) The contacting first adhesive layer (V1-1) or (V1) contains an acrylic resin, so the surface of the first adhesive layer (V1-1) or (V1) can easily form a concave-convex state.

The content ratio of the acrylic resin in the adhesive resin is 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). , more preferably 50 to 100% by mass, particularly preferably 70 to 100% by mass, most preferably 85 to 100% by mass.

The content of the adhesive resin is preferably 35 to 100% by mass relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V), More preferably, it is 50-100 mass %, Most preferably, it is 60-98 mass %, Most preferably, it is 70-95 mass %.

(crosslinking agent) In one aspect of the present invention, when the adhesive composition (v) is an adhesive resin containing functional groups, it is preferable to further contain a crosslinking agent. The crosslinking agent is capable of reacting with the adhesive resin having a functional group and using the functional group as a crosslinking origin to form crosslinks between the adhesive resins.

The cross-linking agent is, for example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, a metal chelate-based cross-linking agent, and the like. These crosslinking agents may be used alone or in combination of two or more. Among these cross-linking agents, isocyanate-based cross-linking agents are preferable in terms of improving cohesion and adhesion, and being easy to obtain.

The content of the crosslinking agent can be appropriately adjusted by the number of functional groups in the adhesive resin. Generally, relative to 100 parts by mass of the adhesive resin with functional groups, it is preferably 0.01-10 parts by mass, more preferably 0.03- 7 parts by mass, preferably 0.05 to 5 parts by mass.

(tackifier) In one aspect of the present invention, the adhesive composition (v) may further contain a tackifier from the viewpoint of further enhancing the adhesive force. In this specification, "tackifier" refers to a component that can assist in improving the adhesive force of the above-mentioned adhesive resin, and means an oligomer with a mass average molecular weight (Mw) of less than 10,000, which can be compared with The above-mentioned adhesive resins are distinguished. The mass average molecular weight (Mw) of the tackifier is preferably 400-10,000, more preferably 500-8,000, most preferably 800-5,000.

Tackifiers, such as pine resins, terpene resins, styrene resins, pentene, isoprene, piperine, 1,3-pentadiene, etc. C5 series petroleum resins obtained by copolymerization, C9 series petroleum resins obtained by copolymerization of C9 fractions such as indene and vinyltoluene produced by thermal decomposition of naphtha, and hydrogenated resins after hydrogenation.

The softening point of the tackifier is preferably 60-170°C, more preferably 65-160°C, particularly preferably 70-150°C. In addition, in this specification, the "softening point" of a tackifier means a value measured in accordance with JIS K 2531. The tackifier may be used alone, or two or more types different in softening point, structure, etc. may be used in combination. Moreover, when using 2 or more types of plural tackifiers, it is preferable that the weighted average of the softening point of these plural tackifiers is in 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 ingredients of the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V), more preferably It is preferably 0.1 to 50% by mass, particularly preferably 1 to 40% by mass, most preferably 2 to 30% by mass.

(additive for adhesive) In one aspect of the present invention, the adhesive composition (v) may further contain adhesive additives used in general adhesives in addition to the above-mentioned additives within the range that does not impair the effect of the present invention. These adhesive additives include, for example, antioxidants, softeners (plasticizers), antirust agents, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, and the like. Moreover, these additives for adhesive agents may be used individually, respectively, and may use it in combination of 2 or more types. When these additives for adhesives are contained, the content of each additive for adhesives is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, based on 100 parts by mass of the adhesive resin.

Also, when using the support layer (II) of the third aspect having the second adhesive layer (V2) as the expandable adhesive layer, the formation of the second adhesive layer (V2) as the expandable adhesive layer The material is formed from the expandable adhesive composition (v22) further containing heat-expandable particles in the above-mentioned adhesive composition (v). The thermally expandable particles are as described above. The content of the heat-expandable particles is preferably 1 to 70% by mass relative to the total amount (100% by mass) of the active ingredients of the expandable adhesive composition (v22) or the total mass (100% by mass) of the expandable adhesive layer , more preferably 2 to 60% by mass, particularly preferably 3 to 50% by mass, most preferably 5 to 40% by mass.

On the other hand, when the adhesive layer (V) is a non-expandable adhesive layer, the adhesive composition (v) as a material for forming the non-expandable adhesive layer preferably does not contain heat-expandable particles. When heat-expandable particles are contained, the less the content, the better. Relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V), it is relatively It is preferably less than 1% by mass, more preferably less than 0.1% by mass, particularly preferably less than 0.01% by mass, most preferably less than 0.001% by mass.

Also, as shown in the laminates 2a and 2b shown in FIG. 2, a support having a first adhesive layer (V1-1) and a second adhesive layer (V1-2) as a non-expandable adhesive layer For layer (II), at 23°C, the storage shear modulus G'(23) of the first adhesive layer (V1-1) of the non-expandable adhesive layer is preferably 1.0×10 ⁸ Pa or less, More preferably, it is 5.0×10 ⁷ Pa or less, and most preferably, it is 1.0×10 ⁷ Pa or less. When the storage shear modulus G'(23) of the first adhesive layer (V1-1) of the non-expandable adhesive layer is 1.0×10 ⁸ Pa or less, for example, as laminates 2a and 2b shown in FIG. 2 etc., the heat-expandable particles in the expandable base material layer (Y1) are expanded by thermal expansion treatment, and the first adhesive layer (V1-1) that is in contact with the cured resin layer (I') is easy to The surface is uneven. As a result, the interface P between the support layer (II) and the cured resin layer (I') can be formed into a laminate that can be easily separated as a whole with only a little force. Also, at 23°C, the storage shear modulus G'(23) of the first adhesive layer (V1-1) of the non-expandable adhesive layer is preferably 1.0×10 ⁴ Pa or more, more preferably 5.0 ×10 ⁴ Pa or more, particularly 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 according to one aspect of the present invention is preferably at least 30%, more preferably at least 50%, and most preferably at least 70%. When the light transmittance is in the above range, when the curable resin layer (I) is irradiated with energy rays (ultraviolet rays) through the support layer (II), the degree of curing of the curable resin layer (I) can be further increased. The upper limit of the light transmittance at a wavelength of 365 nm is not particularly limited, for example, it may be 95% or less. From the viewpoint of achieving the above-mentioned light transmittance, it is preferable that the base material (Y) and the adhesive layer (V) of the support layer (II) contain no coloring agent. When a coloring agent is contained, the less the content, the better. Relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (v) or the total mass (100% by mass) of the adhesive layer (V), preferably It is less than 1% by mass, more preferably less than 0.1% by mass, most preferably less than 0.01% by mass, most preferably less than 0.001% by mass; and the content of the coloring agent in the base material (Y) relative to the resin The total amount (100% by mass) of the active ingredient of the composition (y) or the total mass (100% by mass) of the substrate (Y) is preferably less than 1% by mass, more preferably less than 0.1% by mass, particularly preferably It is less than 0.01% by mass, most preferably less than 0.001% by mass.

(Seal object) The object to be sealed placed on a part of the surface of the curable resin layer (I), for example, a semiconductor wafer, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, a substrate for a flat panel, and the like.

For example, when the object to be sealed is a semiconductor wafer, a semiconductor wafer with a cured resin layer can be produced by using the anti-warpage laminate of one aspect of the present invention. Conventionally known ones can be used for the semiconductor wafer, and integrated circuits composed of circuit elements such as transistors, resistors, and condensers are formed on the circuit surface. Also, the semiconductor wafer is preferably placed on the inner surface opposite to the circuit surface and covered with a surface of a thermosetting resin layer. In this case, after mounting, the circuit surface of the semiconductor wafer is exposed. The placement of the semiconductor wafer can be performed using a known device such as a flip chip bonder and a die bonder. The layout and number of placements of semiconductor chips can be appropriately determined in accordance with the intended packaging form and production quantity.

[Manufacturing method of warpage-resistant laminate] The warpage-resistant laminate can be produced in the following manner. First, a curable resin composition is applied and dried on a release film to form a curable resin layer (I). When the curable resin layer (I) is composed of two layers, each curable resin composition can be formed on each release film, and the two layers can be laminated by direct bonding to obtain a laminated type. hardening resin layer. The first curable resin layer (X1-1) can also be formed by coating the first curable resin composition on the release film and drying it, and then on the first curable resin layer (X1-1), The second curable resin layer (X1-2) or (X2) is applied and dried to obtain a laminated curable resin layer. Then attach the adhesive layer (V) of the support layer (II) to the above-mentioned curable resin layer (I), or through other adhesive layers different from the support layer (II), the curable resin Layer (I) and support layer (II) are pasted together to obtain a warpage-resistant laminate. The support layer (II) can be coated with an adhesive composition on the release film and dried to form the adhesive layer (V), and then, on the adhesive layer, the resin material constituting the base layer is coated On the adhesive layer, after drying treatment, or by pasting the sheet-like substrate on the adhesive layer to form the substrate layer. When the base layer is composed of multiple layers, after the first base layer is formed, the resin material constituting the second base layer is coated on the first base layer, and after drying, the second base layer is formed. . In the case of a support layer having a second adhesive layer on the second base layer, the adhesive composition may be applied on the second base layer and dried to form the second adhesive layer.

[The first manufacturing method of hardened sealing body] The 1st aspect of the manufacturing method of the cured sealing body of this invention is the method of manufacturing a cured sealing body using the laminated body of 1 aspect of this invention, and it has the following steps (i)-(iv). Step (i): The object to be sealed is placed on a part of the first surface of the curable resin layer (I) included in the anti-warping laminate. Step (ii): The object to be sealed and at least the first surface of the curable resin layer (I) in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material. Step (iii): thermally curing the sealing material to form a cured sealing body including the object to be sealed, and at the same time, thermally curing the curable resin layer (I) to form a cured resin layer (I') to obtain a cured resin layer (I'). sealed body. Step (iv): The heat-expandable particles are subjected to expansion treatment, so that the hardened resin layer (I') and the support layer (II) are separated at the interface to obtain a hardened sealing body with a hardened resin layer.

Fig. 6 is a schematic cross-sectional view illustrating the steps of manufacturing a cured sealing body with a cured resin layer, more specifically, a step of manufacturing a cured sealing body using the anti-warpage laminate 1a shown in Fig. 1(b) cross-sectional pattern diagram. Hereinafter, the above steps will be described with appropriate reference to FIG. 6 .

＜Step (i)＞ In the step (i), an object to be sealed is placed on a part of the surface of the curable resin layer (I) that the anti-warpage laminate of one aspect of the present invention has. In FIG. 6(a), it shows the state where the adhesive surface of the adhesive layer (V1) of the support layer (II) is attached to the support body 50 in the warpage-resistant laminate 1b. In FIG. 6(b), In order to show a part of the surface of the curable resin layer (I), the pattern of the object to be sealed 60 is placed. Also, in FIG. 6, although it is an example of using the laminated body 1b shown in FIG. The anti-warp laminate and the object to be sealed are laminated or placed in this order.

The temperature conditions in the step (i) are preferably carried out at a temperature that does not cause the thermally expandable particles to expand, for example, in an environment of 0-80°C (wherein, the expansion initiation temperature (t) is 60- In the case of 80°C, it is better to carry out in an environment that does not reach the expansion initiation temperature (t).

The support body is preferably attached to the entirety of the adhesive surface of the adhesive layer (V1) of the laminate. Therefore, the support body is preferably in the form of a plate. Also, the area of the adhesive surface of the adhesive layer (V1) and the surface of the support on the side to be attached is preferably greater than or equal to the area of the adhesive surface of the adhesive layer (V1) as shown in FIG. 6 .

The material constituting the support body can be appropriately selected according to the type of object to be sealed, the type of sealing material used in step (ii), etc., taking into consideration required properties such as mechanical strength and heat resistance. Specifically, the material constituting the support body, for example, metal materials such as SUS; non-metallic inorganic materials such as glass and silicon wafers; epoxy resin, ABS resin, acrylic resin, engineering plastics, high-grade engineering plastics, polyamide Resin materials such as amine resin and polyamideimide resin; composite materials such as glass epoxy resin, etc. Among them, SUS, glass, and silicon wafers are preferred. Moreover, examples of engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like. High-end engineering plastics include, for example, polyphenylene sulfide (PPS), polyethersulfide (PES), and polyether-etherketone (PEEK).

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

On the other hand, the object to be sealed placed on a part of the surface of the curable resin layer (I), for example, a semiconductor wafer, a semiconductor wafer, a compound semiconductor, a semiconductor package, an electronic component, a sapphire substrate, a display, a flat panel With substrate etc. In the following description, the object to be sealed 60 will be described using a semiconductor wafer as an example.

When the object to be sealed is a semiconductor wafer, a semiconductor wafer with a cured resin layer can be produced by using the laminated body of one aspect of the present invention. Conventionally known ones can be used for the semiconductor wafer, and integrated circuits composed of circuit elements such as transistors, resistors, and condensers are formed on the circuit surface. Also, the semiconductor wafer is preferably placed on the inner surface opposite to the circuit surface and covered with the surface of the thermosetting resin layer (I). In this case, after mounting, the circuit surface of the semiconductor wafer is exposed. The placement of the semiconductor wafer can be performed using a known device such as a flip chip bonder and a die bonder. The layout and number of placements of semiconductor chips can be appropriately determined in accordance with the intended packaging form and production quantity.

The surface of the curable resin layer (I) of this embodiment (in the example of FIG. 6, the surface opposite to the support layer (II) of the non-expandable thermosetting resin layer (X1)) has a cured When the adhesive force is within the above-mentioned range, when the semiconductor chip 60 of the object to be sealed is bonded to the above-mentioned surface of the curable resin layer (I), the semiconductor chip 60 can be firmly fixed, and positional displacement can be easily prevented. .

Among them, like the laminated body of one aspect of the present invention, the area used for covering the sealing material on a semiconductor wafer with a larger wafer size than FOWLP, FOPLP, etc., is formed not only on the circuit surface of the semiconductor wafer, but also on the sealing material. In the surface area of the package, the package that can also form a wire redistribution layer (RDL) is preferred. Therefore, the semiconductor chip is placed on a part of the surface of the curable resin layer (I), and the plurality of semiconductor chips are preferably placed on the surface in a state of forming rows and rows at a specific distance. It is preferable that the plurality of semiconductor wafers are placed on the surface in a state of forming a matrix of rows and columns at predetermined distances. The distance between semiconductor chips can be appropriately determined in accordance with the intended packaging form and the like.

＜Step (ii)＞ In step (ii), in order to place the object to be sealed on the curable resin layer (I), and the first surface of the curable resin layer (I) on at least the peripheral portion of the object to be sealed, heat-cure Permanent sealing material coating (hereinafter also referred to as "coating treatment"). In the coating process, first, the object to be sealed and at least the peripheral portion of the object to be sealed on the surface of the curable resin layer (I) are covered with a sealing material. Specifically, as shown in FIG. 6( c), a laminated body 1b formed by placing a semiconductor wafer 60 on which an object to be sealed is mounted on a curable resin layer (I) attached to a support body 50 is provided. The forming die 70 is disposed within the frame of the forming die 70 . Then, the sealing material is injected through the injection hole 71 into the molding space 72 formed between the molding die 70 , the laminated body 1b, and the object to be sealed 60 . The sealing material covers the entire exposed surface of the semiconductor wafer 60 as the object to be sealed, and also fills the gaps between the plurality of semiconductor wafers. After the injection of the sealing resin and the molding of the resin are completed, the molding die 70 is removed, and as shown in FIG.

In addition, when injecting the sealing material 80 into the molding space 72 using a resin molding method represented by a transfer molding method in which a resin material is injected into a mold, along the direction of the surface of the curable resin (I), A flow of the sealing material 80 will be generated (please refer to the direction of the arrow in FIG. 6( c )). In the manufacturing method of this aspect, the object to be sealed 60 is fixed by the curable resin layer (I), and when the shear strength of the adherend for measurement of the curable resin layer (I) is in the above-mentioned range, it can be easily The object to be sealed 60 is prevented from shifting or tilting.

The sealing material has the function of protecting the sealing object and its additional elements from the external environment. The sealing material 80 used in the manufacturing method of one aspect of this invention is a thermosetting sealing material containing a thermosetting resin.

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

The coating method, in addition to the transfer molding method, can also be selected from the methods used in the previous sealing step, depending on the type of sealing material. For example, roll lamination, vacuum pressurization, vacuum lamination, Spin coating method, die coating method, compression molding die method, etc.

＜Step (iii)＞ In step (iii), after performing the coating treatment, the sealing material is thermally cured to form a cured sealing body including the object to be sealed. In addition, 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 sealing material 80 , a cured sealing body 85 in which the semiconductor wafer 60 to be sealed is covered with the hardened sealing material 81 can be produced. In this way, the semiconductor chip 60 can be protected by the hard material while maintaining the layout. At this time, in the manufacturing method of this aspect, since the curable resin layer (I) uses the thermosetting resin layer (X1), the starting temperature of its hardening and the hardening starting temperature of the thermosetting sealing material 80 are At the same level, or when the curing start temperatures of the two are different, when heating to the higher curing start temperature, the curing of the sealing material and the bonding of the thermosetting resin layer can be carried out at the same time through one heating. Curing (production of cured thermosetting resin layer (X1')). Therefore, in these cases, the number of heating steps performed for hardening can be reduced, and the manufacturing steps can be further simplified.

Also, in the manufacturing method of this aspect, when the curable resin layer (I) is provided, the difference in shrinkage stress between the two surfaces of the obtained hardened sealing body 85 can be reduced, and the hardened sealing body can be effectively suppressed. 85 The resulting deformation. In particular, since the thermosetting resin layer (X1) is also thermosetting at the same time as the sealing material is thermosetting, the difference in shrinkage stress between the two surfaces of the cured sealing body 85 can be reduced during the curing process, and the More effective suppression of deformation. Also, as described above, the heating temperature used for hardening in step (iii) is lower than the heating temperature used for expansion in step (iv).

＜Step (iv)＞ In step (iv), when the heat-expandable particles contained in the expandable substrate layer (Y1) are subjected to expansion treatment, the hardened resin layer (I') and the support layer (II) can be separated at the interface to obtain Hardened seal with hardened resin layer. Figure 6(f) shows that after the heat-expandable particles are expanded, the expandable substrate layer (Y1) becomes the expanded expandable substrate layer (Y1'), and the cured resin layer (I') and the expanded The interface of the subsequent support layer (II') is separated. As shown in Fig. 6(f), a hardened sealing body with a hardened resin layer (I') having a hardened sealing body 85 in which the object to be sealed 60 is sealed and a hardened resin layer (I') is obtained by forming a separation result at the interface. 200. In addition, the presence of the cured resin layer (I') has the function of effectively suppressing the deformation caused by the cured sealing body, thereby improving the reliability of the sealed object.

The "expansion treatment" in step (iv) is to heat the thermally expandable particles above the expansion initiation temperature (t) to undergo expansion treatment, and then through this treatment, the support layer on the side of the hardened resin layer (I') (II) has irregularities on the surface. As a result, the interface P can be easily separated as a whole with a little force. The "temperature above the expansion initiation temperature (t)" for thermally expandable particles to expand is preferably above the "expansion initiation temperature (t) + 10°C" and below the "expansion initiation temperature (t) + 60°C" , "expansion initiation temperature (t) + 15°C" or more and "expansion initiation temperature (t) + 40°C" or less are preferred. Again, the heating method for making the thermally expandable particles expand is not particularly limited, for example, heating methods such as a heating plate, an oven, a sintering furnace, an infrared lamp, a hot air blower, etc. can be used to make the support layer (II) and hardened From the viewpoint that the interface P of the resin layer (I′) is easily separated, it is preferable that the heat source during heating be provided on the side of the support body 50 .

The hardened sealing body 200 with the hardened resin layer obtained in this way is then subjected to necessary processing. The cured resin layer of the deformation correction layer can be removed by grinding or the like during the process to the final semiconductor device, and will not remain in the final semiconductor device.

[Second manufacturing method of hardened sealing body] The second aspect of the method for producing a cured sealing body of the present invention is a method for producing a cured sealing body using the laminate of one aspect of the present invention, which includes the following steps (i') to (iv). Step (i'): One of the surfaces of the energy ray-curable resin layer (X2) on the first surface of the curable resin layer (I) of the warpage-resistant laminate that is opposite to the first layer part, mount the sealed object. Step (ii')-1: Irradiating energy rays to harden the energy ray-curable resin layer (X2). Step (ii')-2: The object to be sealed and at least the first surface of the curable resin layer in the peripheral portion of the object to be sealed are covered with a thermosetting sealing material. Step (iii'): thermally curing the sealing material to form a cured sealing body including the aforementioned object to be sealed, and at the same time, thermally curing the curable resin layer (I) to form a cured resin layer (I') to obtain a cured resin layer (I'). sealed body. Step (iv): The expandable particles are subjected to expansion treatment, so that the hardened resin layer (I') and the support layer (II) are separated at the interface to obtain a hardened sealing body with a hardened resin layer.

Below, each step will be described in detail, but in order to avoid being too redundant, when the steps or operations are the same as the first aspect of the above-mentioned manufacturing method, the content described in the first aspect of the manufacturing method will be replaced, and the detailed description will be omitted. .

＜Step (i')＞ In the step (i'), an object to be sealed is placed on a part of the surface of the curable resin layer (I) included in the anti-warpage laminate according to one aspect of the present invention. In Fig. 7(a), the curable resin layer (I) uses the thermosetting resin layer (X1-1) on the support layer (II) side, and the energy ray curable resin on the opposite side to the support layer (II) The anti-warping laminate 5 (please refer to Fig. 5) composed of layer (X2) is the state where the adhesive surface of the adhesive layer (V1) of the support layer (II) is attached to the support 50, as shown in Fig. 7(b ) shows a state where the object to be sealed 60 is placed on a part of the surface of the curable resin layer (I).

The surface of the curable resin layer (I) of this embodiment (in the example of FIG. 7, the surface of the energy ray curable resin layer (X2) opposite to the support layer (II)) has curability. In other words, the adhesive force is as follows: after attaching the above-mentioned first surface to the glass plate at a temperature of 70°C, the hardening resin layer ( I) When the value measured during peeling is 1.7N/25mm or more, when the sealing object 60 is bonded to the above-mentioned surface of the curable resin layer (I), the sealing object 60 can be firmly fixed, and it is easy to prevent inclusion. Positional deviation of tilt, offset, etc.

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

Figure 7(c) shows that in this step, the cured energy ray curable resin layer (X2') is formed by curing the energy ray curable resin layer (X2), and a part of the cured resin layer (X2') is formed. (That is, the layer on the first surface side is hardened) The state of the hardened resin layer (I*). The type and irradiation conditions of energy rays are not particularly limited as long as they can harden the energy ray-curable resin layer (X2) to the extent that it can fully exert its functions. They can be combined with known methods. The desired process is appropriately selected for use. The material constituting the energy ray curable resin layer (X2) can be selected more broadly when the ultraviolet ray curable resin composition is used, and the source of the energy ray to harden the composition can be easily obtained and Ultraviolet irradiation device with excellent handling properties. When the energy ray curable resin layer (X2) is cured, the illuminance of the energy ray is preferably 4-280mW/cm ² , and the illuminance of the energy ray is preferably 3-1,000mJ/cm ² during the aforementioned curing.

Before the step (iii') including thermosetting, by irradiating energy rays in the step (ii')-1, it is possible to avoid cracking of the energy ray-curable resin due to heating and accelerate the hardening reaction, so that the The hardening reaction of the energy line proceeds more efficiently. In addition, it is also possible to prevent the low-molecular components (photopolymerization initiator, etc.) contained in the energy ray curable resin from being volatilized by heating and contaminating the object to be sealed. In addition, before thermosetting, the energy ray-curable resin layer is hardened with energy rays, which can prevent the energy ray-curable resin (X2) from shrinking due to heat treatment due to thermosetting, and can prevent the sealing resin from collapsing with energy. Adhesion between the line-curable resins (X2) decreases.

＜Step (ii')-2＞ After arranging the sealing object 60, irradiating energy rays, etc. to form a cured energy ray-curable resin layer (X2'), in step (ii')-2, follow the same description as that of FIG. 6(d) , inject the sealing material 80 using a molding die not shown in the drawings. At this time, although flow of the sealing material in the surface direction occurs, the object to be sealed 60 is fixed by the cured energy ray curable resin layer (X2'), and the measurement using the curable resin layer (I) A silicon wafer with a mirror surface and a thickness of 350 μm with a shear strength of the adherend of 3mm×3mm is used as the above-mentioned adherend for measurement. When the mirror surface of the body is pressed against the curable resin layer (I) and pasted, the value measured at a speed of 200 μm/s is 20 N/(3mm×3mm) or more, and the deflection of the sealing object 60 can be easily prevented. shift or tilt. When the injection of the sealing resin is completed, the surface of the hardening energy ray-curable resin layer (X2') of the sealing object 60 and its periphery is covered with the sealing material 80 as shown in FIG. 7(d).

＜Step (iii')＞ In step (iii'), after performing the coating treatment, the sealing material is thermally cured to form a cured sealing body including the object to be sealed. In addition, 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 layer and the second layer are cured is formed. As a result of hardening of the sealing material 80 , as shown in FIG. 7( e ), a hardened sealing body 85 in which the object 60 to be sealed is covered with the hardened sealing material 81 is formed. At this time, in this production example, since the curable resin layer (I) uses the thermosetting resin layer (X1-1), the temperature of the thermosetting sealing material 80 is about the same as the curing start temperature, or the curing start temperature When the temperatures are different, when heating to a higher curing start temperature or higher, the curing of the sealing material and the curing of the thermosetting resin layer can be simultaneously performed through one heating.

＜Step (iv)＞ In the step (iv), the cured resin layer (I') and the support layer (II) are separated at the interface through the treatment of expanding the expandable particles contained in the expandable substrate layer (Y1), thereby obtaining Hardened seal with hardened resin layer. Fig. 7 (f) is, expandable particle is through expanding treatment, and makes expandable base material layer (Y1) form expandable base material layer (Y1'), makes cured resin layer (I') and support layer after expansion ( The interface of II') is in a state of separation. As shown in Fig. 7(f), the separation result is formed through the interface, and the hardened sealing body 85 having the sealed object 60 sealed, and the hardened resin layer (I') with the hardened resin layer are obtained. Sealing body 201.

After the hardened sealing body 85 is manufactured according to the above procedures, necessary processing can be performed on the hardened sealing body 201 with the hardened resin layer. [Example]

Subsequently, the present invention will be described using specific examples, but the present invention is not limited by these illustrations. In addition, in the following description, curable resin layer (I) includes both "energy ray curable resin layer (X2)" and "thermosetting resin layer (X1-1), (X1-2)", etc. meaning. In addition, the physical property value in the following manufacture example and an Example is the value measured by the following method.

＜Mass average molecular weight (Mw)＞ Using a gel permeation chromatography analyzer (manufactured by Tosoh Co., Ltd., product name "HLC-8020"), the measurement was performed under the following conditions, and the measured values converted to standard polystyrene were used. (measurement conditions) ・Tube column: Connect "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL" and "TSK gel G1000HXL" in sequence (all of which are manufactured by Tosoh Co., Ltd.) ・Column temperature: 40°C ・Developing solvent: Tetrahydrofuran ・Flow rate: 1.0mL/min

＜Measurement of thickness of each layer＞ The measurement was performed using a constant pressure thickness measuring device (model: "PG-02J", standard specification: based on JIS K6783, Z1702, Z1709) manufactured by TECLOCK Co., Ltd.

<Minimum curing temperature of curable resin layer> Using the same composition to prepare a plurality of measurement samples in advance, and then using a differential scanning thermal analyzer (manufactured by TA Instruments, Q2000), set the temperature step by step between 60°C and 20°C, and measure the respective The time from peak of hardening reaction to disappearance. At this time, the temperature was raised from normal temperature to the set temperature at a temperature increase rate of 10° C./min. In the above-mentioned measurement, the temperature at which the peak of the curing reaction disappeared after 2 hours was set as the lowest curing temperature. ＜Releasability of cured resin layer after hardening＞ Prepare 2 glass plates (3 mm float glass (JIS R3202 product) manufactured by U-KOU Chamber of Commerce Co., Ltd.) with a support layer attached to a curable resin layer as samples, one of which is heated at 130° C. for 2 hours, and the other Those were heated at 160°C for 1 hour. For the heated measurement samples, the support layer of each sample was heated at the maximum expansion temperature +30° C. described later for 3 minutes using a hot plate. After cooling to room temperature, evaluate the peelability of the support layer and the hardened resin layer. When the curable resin layer does not peel off from itself (peeling without external force), use nickel to pinch the end of the curable resin layer to form peeling at the interface between the support layer and the curable resin layer, and evaluate it. ○=The whole body peeled off from the body, and no abnormality was found in the appearance of the peeled surface of the cured resin layer. △=Tweezers must be used to peel off, and part of the interface P cannot be peeled off. No abnormality was found in the appearance of the peeled surface of the cured resin layer. × = It cannot be peeled off even with tweezers, or the hardened resin layer has areas where it cannot be peeled off all over.

<Measurement of expansion initiation temperature (t) and maximum expansion temperature of heat-expandable particles> The expansion initiation temperature (t) of the heat-expandable particles used in each example was measured by the following method. Made in an aluminum cup with a diameter of 6.0mm (inner diameter 5.65mm) and a depth of 4.8mm, add 0.5mg of heat-expandable particles to be measured, and cover the sample with an aluminum cap (diameter 5.6mm, thickness 0.1mm). Using a dynamic viscoelasticity measurement device, measure the height of the sample from the upper part of the aluminum cover of the sample with a force of 0.01N applied by a presser. Then, in the state where a force of 0.01N is applied to the press, heat it from 20°C to 300°C at a heating rate of 10°C/min, and measure the displacement in the vertical direction of the press. The displacement start temperature in the direction is set as the expansion start temperature (t). Also, the maximum expansion temperature refers to the temperature at which the above-mentioned displacement reaches the maximum.

<Measurement of the expansion coefficient of the support layer between the curing temperature of the curable resin layer> The amount of displacement obtained when the above-mentioned maximum expansion temperature was measured was defined 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 was heated under the hardening condition 1 (heating at 130°C for 2 hours) of the curable resin layer was measured, and the thickness (Da) of the support layer was different from that under the hardening condition 2 (heating at 160°C) of the curable resin layer. 1 hour) The thickness of the support layer (Db) when heated. Subsequently, the values of (Da/Dm)×100 and (Db/Dm)×100 were calculated as the expansion ratio of the support layer of the curable resin layer at the curing temperature.

＜Measurement of Adhesion of Thermosetting Resin Layer＞ An adhesive tape (manufactured by Linde Corporation, product name "PL-SHIN") was laminated on the surface of the thermosetting resin layer formed on the release film. Then, the release film was removed, and the exposed surface of the thermosetting resin layer was attached to the smooth surface of a glass plate (3 mm float glass (JIS R3202 product) manufactured by U-KOU Shokai Co., Ltd.) as an adherend. The sticking temperature of this thermosetting resin layer (X1) was set to 70 degreeC. Subsequently, the above-mentioned glass plate with each layer was left to stand for 24 hours at 23°C and 50% RH (relative humidity), and then stretched at 180° under the same environment based on JIS Z0237:2000 Peeling method, under the condition of tensile speed 300mm/min, measure the adhesive force at 23°C.

In addition, the peeling materials used in the following production examples are as follows. ・Heavy release film: Linde Co., Ltd., product name "SP-PET382150", a polyethylene terephthalate (PET) film with a release agent made of a silicone release agent on one side Layer, thickness: 38μm ・Light release film: Linde Co., Ltd., product name "SP-PET381031", PET film with a release agent layer formed of a silicone release agent on one side, thickness: 38 μm

＜Evaluation of deformation＞ The thermosetting resin layers of the anti-warpage laminates of Examples 1 and 2 were respectively attached to a 12-inch silicon wafer with a thickness of 100 μm, on the opposite side to the surface on which the thermosetting resin layer was attached. An epoxy resin composition was applied to a thickness of 30 μm. Subsequently, the layer of the above-mentioned epoxy resin composition and the thermosetting resin layer of each laminate were heated to be hardened. After curing, place the silicon wafer with the cured resin layer on the horizontal platform, observe visually, and evaluate whether there is deformation according to the following criteria. A: The amount of deformation is 3 mm or less. B: The amount of deformation is greater than 3 mm and less than 15 mm. C: The amount of deformation is 15 mm or more. The above-mentioned epoxy resin composition is a mixture of "EPO-FIX resin" manufactured by STRUERS and "EPO-FIX hardener" manufactured by the same company. Also, in this evaluation, from the viewpoint of simplifying the experimental procedure, a large-diameter silicon wafer was used as the attached body. Conditions to form an evaluation suitable for use in deformation.

Manufacturing example 1 (1) Manufacture of curable resin composition Blend the ingredients of the types and amounts shown below (all of which are "active ingredient ratios"), dilute with methyl ethyl ketone, and stir uniformly to obtain a solid ingredient concentration (active ingredient concentration) of 61 Mass % solution of thermosetting resin composition. ・Acrylic polymer: Addition amount = 21 parts by mass Acrylic polymer (mass Average molecular weight: 800,000, glass transition temperature: -28°C), and correspond to the above-mentioned component (A1). ・Epoxy compound (1): Addition amount = 10 parts by mass Liquid bisphenol A type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name "BPA328", epoxy equivalent = 220 to 240 g/eq) corresponds to the above-mentioned component (B1). ・Epoxy compound (2): Addition amount = 2.0 parts by mass A solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "EPIKOTE 1055", epoxy equivalent = 800 to 900 g/eq) corresponds to the above-mentioned component (B1). ・Epoxy compound (3): Addition amount = 5.6 parts by mass Dicyclopentadiene-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "XD-1000L", epoxy equivalent = 274 to 286 g/eq) corresponds to the above-mentioned component (B1). ・Thermal curing agent: Addition amount = 0.5 parts by mass Dicyandiamide (manufactured by ADEKA Corporation, product name "ADEKA Hardener EH-3636AS", active hydrogen content = 21 g/eq) corresponds to the above-mentioned component (B2). ・Hardening accelerator: Added amount = 0.5 parts by mass 2-Phenyl-4,5-dimethylolimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "CUREXOL 2PHZ") corresponds to the above-mentioned component (B3). ・Silane coupling agent: Addition amount = 0.4 parts by mass An epoxy group-containing oligomer type silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2") corresponds to the above-mentioned component (D). ・Inorganic filler (1): Addition amount = 6 parts by mass Spherical silica filler (manufactured by ADMATECHS, product name "SC2050MA", average particle diameter = 0.5 μm) corresponds to the above-mentioned component (E). ・Inorganic filler (2): Addition amount = 54 parts by mass Spherical silica filler (manufactured by Tatsumori Co., Ltd., product name "SV-10", average particle diameter = 8 μm) corresponds to the above-mentioned component (E).

(2) Formation of thermosetting resin layer On the release-treated surface of the above-mentioned light-release film, apply the solution of the thermosetting resin composition prepared in the above (1) to form a coating film, and dry the coating film at 120°C for 2 minutes to form a thickness 25 μm thermosetting resin layer. Let this be the curable resin layer 1 . Moreover, the adhesive force of the formed thermosetting resin layer 1 was 0.5N/25mm.

Manufacturing example 2 (1) Fabrication of the support layer A heat-peelable laminate (made by Nitto Denko Co., Ltd., product name) having a structure in which a heat-peelable adhesive layer is provided on a polyester film substrate "REVALPHA (NITTO 3195)") is used as a support layer. Make it support layer 1. Moreover, when producing the laminated body for anti-warping mentioned later, the release liner provided on the surface of a heat release adhesive layer can be peeled off and used. The support layer 1 is an adhesive layer having a substrate and heat-expandable particles. When heated to an expansion initiation temperature of 170° C. or higher, the heat-expandable particles will expand and produce fine unevenness on the surface of the adhesive layer. .

Manufacturing example 3 (1) Synthesis of urethane prepolymer In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate, the hydroxyl group of the carbonate diol and isophor The equivalent ratio of the isocyanate group of ketone diisocyanate is 1/1, then add 160 parts by mass of toluene, under nitrogen atmosphere, stirring, until the concentration of isocyanate group reaches the theoretical amount, carry out at 80°C for 6 hours above reaction. Next, a solution obtained by diluting 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added until the isocyanate groups at both ends disappeared, and then carried out at 80°C. After 6 hours of reaction, a urethane prepolymer with a mass average molecular weight of 29,000 was obtained.

(2) Synthesis of urethane acrylate resin In the reaction vessel under nitrogen atmosphere, add 100 parts by mass (solid content ratio) of the urethane prepolymer obtained in Production Example 1, and 117 parts by mass (solid content ratio) of methyl methacrylate (MMA) , 2-hydroxyethyl methacrylate (2-HEMA) 5.1 mass parts (solid content ratio), 1-thioglycerol 1.1 mass parts (solid content ratio), and toluene 50 mass parts, in stirring, be warming up to 105 until ℃. Subsequently, in the reaction vessel, the solution diluted with 210 parts by mass of toluene of 2.2 parts by mass (solid content ratio) of a free radical initiator (manufactured by Japan Finechem Co., Ltd., product name "ABN-E") was maintained at At 105°C, it was dropped therein over 4 hours. After completion|finish of dripping, reaction was performed at 105 degreeC for 6 hours, and the solution of the urethane acrylate resin with a mass average molecular weight of 105,000 was obtained.

(3) Manufacture of adhesive composition (1) Mix 5.0 parts by mass (solid content ratio) of the following isocyanate-based crosslinking agent (i) with 100 parts by mass of the following acrylic copolymer (i) as an adhesive resin, dilute with toluene, and stir uniformly Then, an adhesive composition (1) having a solid content concentration (active ingredient concentration) of 25% by mass was obtained. ・Acrylic copolymer (i): Has a structure derived from raw material monomers consisting of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) Acrylic copolymer with a mass average molecular weight of 600,000 per unit. ・Isocyanate crosslinking agent (i): manufactured by Tosoh Co., Ltd., product name "CORONATE L", solid content concentration: 75% by mass.

(4) Manufacture of adhesive composition (2) Mix 5.0 parts by mass (solid content ratio) of the following isocyanate-based crosslinking agent (i) with 100 parts by mass of the following acrylic copolymer (i) as an adhesive resin, dilute with toluene, and stir uniformly Thereafter, an adhesive composition (2) having a solid content concentration (active component concentration) of 25% by mass was prepared. ・Acrylic copolymer (i): Has a structure derived from raw material monomers consisting of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA) = 80.0/20.0 (mass ratio) Acrylic copolymer with a mass average molecular weight of 600,000 per unit. ・Isocyanate crosslinking agent (i): manufactured by Tosoh Co., Ltd., product name "CORONATE L", solid content concentration: 75% by mass.

(5) Formation of adhesive layer (1) On the surface of the release agent layer of the above-mentioned light release film, apply the adhesive composition (1) prepared according to Production Example 3 (1) to form a coating film, and dry the coating film at 100°C for 60 seconds. An adhesive layer (1) having a thickness of 5 μm was formed. (6) Formation of adhesive layer (2) On the surface of the release agent layer of the above-mentioned heavy-release film, apply the adhesive composition (2) prepared according to Production Example 3 (2) to form a coating film, and dry the coating film at 100°C for 60 seconds. An adhesive layer (2) having a thickness of 10 μm was formed.

(7) Production of support layer On one side of a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "COSMO-SHUNE A4100") with a thickness of 50 μm as a base material, stick The above adhesive layer (2). Then, on the other side of the above PET film, apply to 100 parts by mass of polyester adhesive (glass transition temperature: -50°C, mass average molecular weight: 21,000, OH value: 4mgKOH/g), add HDI isocyanate The composition obtained with 4 parts by mass of the urate crosslinking agent was dried at 100° C. for 1 minute to form an anchor layer with a thickness of 40 μm. In 100 parts by mass of the solid content of the urethane acrylate resin obtained in Production Example 3 (2), an isocyanate-based crosslinking agent (manufactured by Tosoh Co., Ltd., product name "CORONATE L", solid content Concentration: 75% by mass) 6.3 parts by mass (solid content ratio), 1.4 parts by mass (solid content ratio) of dioctyltin bis(2-ethylhexanoate) as a catalyst, and the above-mentioned thermally expandable particles (KUREHA Co., Ltd. Co., Ltd., product name "S2640", expansion initiation temperature (t) = 208°C, average particle size (D ₅₀ ) = 24 μm, 90% particle size (D ₉₀ ) = 49 μm), diluted with toluene and stirred uniformly , and a resin composition having a solid content concentration (active component concentration) of 30% by mass was obtained. The content of the thermally expandable particles was 20% by mass based on the total amount (100% by mass) of active ingredients in the obtained resin composition. The resin composition containing the heat-expandable particles was coated on the above-mentioned anchor layer to form a coating film, and the coating film was heat-dried at 100° C. for 2 minutes to form a heat-expandable layer with a thickness of 35 μm. The above-mentioned adhesive layer (1) is pasted on the heat-expandable layer. In this way, a support layer with a release film laminated on the front and back was produced. Make it support layer 2. The support layer 2 is a base material with an adhesive layer and heat-expandable particles. When heated above 208° C., the heat-expandable particles can expand to form fine uneven shapes on the surface of the support layer.

Manufacturing Example 4 Except for changing the heat-expandable particles to heat-expandable microcapsules manufactured by Japan Ferrite Co., Ltd. (product name "Expancel 031-40DU", expansion initiation temperature (t) = 80°C), drying conditions after coating the resin composition to form a coating film The support layer was prepared in the same procedure as that of Production Example 3 except that the temperature was changed to 100° C. for 1 minute. Make it support layer 3. Since the support layer 3 is a base material with an adhesive layer and heat-expandable particles, the heat-expandable particles can expand when heated above 80° C., thereby forming fine uneven shapes on the surface of the support layer.

Manufacturing Example 5 In addition to changing the heat-expandable particles to heat-expandable microcapsules from Japan Ferrite Co., Ltd. (product name "Expancel 053-40DU", expansion initiation temperature (t) = 100°C), and changing the drying conditions after coating the resin composition to form a coating film Except for 1 minute at an ambient temperature of 100°C, the support layer was prepared in the same procedure as in Production Example 3. Make it support layer 4. Since the support layer 4 is a substrate having an adhesive layer and heat-expandable particles, when heated above 100° C., the heat-expandable particles can be expanded to generate fine unevenness on the surface of the support layer. Also, in Production Examples 4 and 5, when the support layer was produced, although the drying temperature after coating the resin composition to form a coating film was higher than the expansion initiation temperature (t) of the heat-expandable particles, the above drying temperature The temperature is ambient temperature, so foaming does not occur on the formed support layer.

Manufacturing example 6 The heat-removing expandable particles use heat-expandable microcapsules manufactured by Japan Ferrite Co., Ltd. (product name "Expancel 920-40DU", expansion initiation temperature (t) = 120°C), and the drying conditions after coating the resin composition to form a coating film are changed to At an ambient temperature of 100° C., except for 1 minute, the support layer was prepared in the same procedure as in Production Example 3. Make it support layer 5. Since the support layer 5 is a substrate having an adhesive layer and heat-expandable particles, when heated above 120° C., the heat-expandable particles can be expanded to generate fine unevenness on the surface of the support layer.

(Example 1) Remove the peeling film laminated on the adhesive layer (2) of the support layer 2 obtained in Production Example 3, so that the adhesive surface of the exposed adhesive layer (2) and the curable resin formed according to Production Example 1 The surface of layer 1 is attached to form a sequential lamination of heavy release film/adhesive layer (1)/substrate/anchor layer/thermal expansion layer/adhesive layer (2)/thermosetting resin layer/peeling film Anti-war laminate with release film.

(Example 2) Remove the release film laminated on the adhesive layer of the support layer 1 in Production Example 2, and make the exposed adhesive surface of the adhesive layer (2) adhere to the surface of the curable resin layer 1 formed according to Production Example 1 , to obtain a warpage-resistant laminate with a release film laminated in the order of base material/adhesive layer/thermosetting resin layer/release film.

(comparative example 1) Remove the release film laminated on the second adhesive layer of the support layer 3 obtained in Production Example 4, so that the adhesive surface of the exposed adhesive layer (2) is the same as the curable resin layer 1 formed in Production Example 1. Laminated in the order of heavy release film/adhesive layer (1)/substrate/anchor layer/thermal expansion layer/adhesive layer (2)/thermosetting resin layer/peeling film Anti-warping laminate with release film.

(comparative example 2) Remove the release film laminated on the second adhesive layer of the support layer 4 obtained in Production Example 5, so that the adhesive surface of the exposed adhesive layer (2) is the same as the curable resin layer 1 formed in Production Example 1. Laminated in the order of heavy release film/adhesive layer (1)/substrate/anchor layer/thermal expansion layer/adhesive layer (2)/thermosetting resin layer/peeling film Anti-warping laminate with release film.

(comparative example 3) Remove the release film laminated on the adhesive layer (2) of the support layer 5 obtained in Production Example 6, so that the adhesive surface of the exposed adhesive layer (2) is the same as the curable resin layer formed in Production Example 1. 1 surface bonding, and obtained by lamination of the sequence of release film/adhesive layer (1)/substrate/anchor layer/thermal expansion layer/adhesive layer (2)/thermosetting resin layer/peeling film Anti-warping laminate with release film.

The warpage-resistant laminates obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were measured and evaluated according to the above-mentioned measurement method and evaluation procedure. The results are shown in Table 1.

It can be clearly seen from the results in Table 1 that in Examples 1 and 2, when the curable resin layer is cured at 130°C for 2 hours, the cured resin layer and the support layer have good peelability and fully suppress warpage happened. Also, in Examples 1 and 2, even when the curable resin layer is cured at 160° C. for 1 hour, the peelability between the cured resin layer and the support layer can still be maintained to a practical level, and warpage can also be sufficiently suppressed. The occurrence of the song. Especially compared to Example 2 when hardening at 160°C, although the support layer foams to some extent and the peelability of the support layer is also slightly reduced, the performance of Example 1 in peelability and warpage In any evaluation, it is the same as the case of curing at 130° C., and a cured sealing body can be produced in a shorter time. On the other hand, in Comparative Examples 1 to 3, the detachability between the curable resin layer and the support layer was greatly reduced, and the interface between the support layer and the cured resin layer could not be delaminated.

(I)‧‧‧hardening resin layer (I')‧‧‧hardening resin layer (I ^* )‧‧‧hardening resin layer partially cured (II)‧‧‧support layer (II')‧‧ ‧Support layer after expansion (V)‧‧‧Adhesive layer (V1)‧‧‧(1st) adhesive layer (V1-1)‧‧‧1st adhesive layer (V2), (V1-2) ‧‧‧The second adhesive layer (X1), (X1-1), (X1-2)‧‧‧thermosetting resin layer (X1')‧‧‧hardened thermosetting resin layer (X1-1' )‧‧‧hardened thermosetting resin layer (X2)‧‧‧energy ray curable resin layer (X2')‧‧‧cured energy ray curable resin layer (Y)‧‧‧substrate (Y1)‧ ‧‧Expandable substrate layer (Y1')‧‧‧Expanded expandable substrate layer (Y2)‧‧‧Non-expandable substrate layer 1a, 1b, 2a, 2b, 3, 4, 5‧‧‧ Warpage-resistant laminate 50‧‧‧support body 60‧‧‧sealed object (semiconductor wafer) 70‧‧‧molding die 71‧‧‧injection hole 72‧‧‧molding space 80‧‧‧sealing material 81‧‧ ‧Hardened sealing material 85‧‧‧Hardened sealing body 200‧‧‧Hardened sealing body P with hardened resin layer‧‧‧Interface

[ Fig. 1] Fig. 1 is a schematic cross-sectional view showing the configuration of the anti-warp laminate according to the first aspect of the present invention. [ Fig. 2] Fig. 2 is a schematic cross-sectional view showing the configuration of the anti-warping laminate according to the second aspect of the present invention. [ Fig. 3] Fig. 3 is a schematic cross-sectional view showing the composition of the anti-warping laminate according to the third aspect of the present invention. [ Fig. 4] Fig. 4 is a schematic cross-sectional view showing the configuration of a warpage-resistant laminate according to a fourth aspect of the present invention. [ Fig. 5] Fig. 5 is a schematic cross-sectional view showing the configuration of an anti-warping laminate according to a fifth aspect of the present invention. [ Fig. 6 ] A schematic cross-sectional view showing steps of manufacturing a cured sealing body with a cured resin layer. [ Fig. 7] Fig. 7 is a schematic sectional view showing another step of manufacturing a cured sealing body with a cured resin layer.

(I)‧‧‧curable resin layer

(II)‧‧‧support layer

(V)‧‧‧adhesive layer

(V1)‧‧‧(1st) adhesive layer

(X1)‧‧‧thermosetting resin layer

(Y)‧‧‧Substrate

(Y1)‧‧‧expandable substrate layer

(Y2)‧‧‧Non-expandable substrate layer

1a, 1b‧‧‧Warpage-resistant laminates

P‧‧‧Interface

Claims (10)

A warpage-resistant laminate for a cured sealing body, characterized by having a curable resin layer (I) comprising 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, the support layer (II) has a base material (Y) and an adhesive layer (V), and the base material (Y) and the adhesive layer (V) At least one of them includes heat-expandable particles, curable resin layer (I), adhesive layer (V), and substrate (Y), while being arranged in this order, the aforementioned adhesion of the curable resin layer (I) The surface is arranged on the opposite side to the adhesive layer (V), and the curing of the curable resin layer (I) is completed within 2 hours to form the minimum curing temperature (T ₁ ) of the cured resin layer (I'), which is higher than the above The foaming initiation temperature (T ₂ ) of the heat-expandable particles is lower. It is in the aforementioned adhesive surface of the curable resin layer (I) to seal the object to be sealed. The minimum hardening temperature of the curable resin layer (I) is ( The difference (T ₂ −T 1 ) between T ₁ ) and the foaming initiation temperature (T ₂ ) of _the thermally expandable particles is 20°C to 100°C. The warpage-resistant laminate according to claim 1, wherein the difference between the lowest curing temperature (T ₁ ) of the curable resin layer (I) and the foaming initiation temperature (T ₂ ) of the thermally expandable particles (T ₂ -T ₁ ) 20°C~90°C. As in the anti-warping laminate of claim 1 or 2, the curable resin layer (I) has two or more thermosetting resin layers (X1), and the two or more thermosetting resin layers (X1) The minimum value (T _1a ) of the lowest hardening temperature (T ₁ ) is lower than the above-mentioned foaming initiation temperature (T ₂ ) of the thermally expandable particles. The laminate according to claim 1 or 2, wherein the thermosetting resin layer (X1) has a thickness of 1 to 500 μm. The laminate according to claim 1 or 2, wherein the base material (Y) is an expandable base material layer (Y1) containing the aforementioned heat-expandable particles. The laminate according to claim 5, wherein the adhesive layer (V) is a non-expandable adhesive layer. The laminate according to claim 5, wherein the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1), and the support layer (II) has a non-expandable base material layer in sequence layer (Y2), expandable substrate layer (Y1), and adhesive layer (V). The warpage-resistant laminate according to claim 1 or 2, wherein 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 aforementioned first layer is a thermosetting resin layer (X1-1), The second layer is an energy ray curable resin layer (X2). A method of manufacturing a hardened sealing body, which is a method of manufacturing a hardened sealing body using the anti-warp laminate according to any one of claims 1 to 7, characterized in that it is included in the hardening of the anti-warp laminate Part of the adhesive surface of the permanent resin layer (I), the step of placing the object to be sealed, and the aforementioned adhesion of the object to be sealed to at least the peripheral part of the hardened resin layer (I) of the object to be sealed In the step of covering the surface with a thermosetting sealing material, while thermosetting the sealing material to form a hardened sealing body including the sealing object, the curable resin layer (I) is also thermoset to form a cured resin layer, and the step of making a hardened sealing body with a hardened resin layer. A method of manufacturing a cured sealing body, which is a method of manufacturing a cured sealing body using the anti-warping laminate of claim 8, characterized in that it is included in the curable resin layer (I) that the anti-warping laminate has A part of the adhesive surface of the sealing object, the step of placing the object to be sealed, the step of irradiating energy rays to harden the energy ray curable resin layer (X2), and the step of bonding the object to be sealed to at least the peripheral portion of the object to be sealed The step of covering the aforementioned adhesive surface of the curable resin layer (I) with a thermosetting sealing material, and thermosetting the aforementioned sealing material to form a hard surface containing the aforementioned sealing object. Simultaneously with the curing of the sealing body, the curable resin layer (I) is also thermally cured to form the hardening resin layer (I') to obtain a hardening sealing body with a hardening resin layer.

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