TWI793186B - Method for producing laminate and hardened seal - Google Patents

Abstract

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

Description

Method for producing laminate and hardened seal

The present invention relates to a method of manufacturing a laminated body and a 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 FOWLP and FOPLP, for example, a hardened sealing body can be produced by placing a plurality of semiconductor wafers on a temporary fixing sheet, covering with a thermosetting sealing material, and thermosetting the sealing material. The hardening step, the separation step of separating the hardened sealing body from the temporary fixing sheet, and the wire redistribution layer (RDL) forming step of forming a wire redistribution layer (RDL) on the surface of the exposed semiconductor wafer side Manufactured (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 technical literature] [Patent literature]

[Patent Document 1] Patent No. 3594853

[Problem to be solved by the invention]

However, when the hardened sealing body described in Patent Document 1 is manufactured using the adhesive sheet as the temporary fixing sheet, the hardened sealing body tends to warp when subjected to heat shrinkage. At this point, it is speculated that because of being sealed in the semiconductor wafer in the hardened sealing body, there is a surface side adjacent to the temporary fixing sheet, so in the hardened sealing body, the thermal expansion coefficient is small but exists in the semiconductor wafer. The area on the side with a relatively higher ratio and the area on the side with a higher thermal expansion coefficient and a relatively higher ratio of hardened resin are caused by the stress generated by the difference in thermal contraction rate between the two areas. This problem tends to become more prominent as the package size of FOWLP, FOPLP, etc. increases. The warped hardened seal, for example, will be prone to breakage when the hardened seal is ground in the subsequent step, and when the hardened seal is transported by the device, it will be prone to misalignment when the hardened seal is received and delivered by the arm. question.

As for the method of suppressing the deformation of the hardened sealing body, for example, a method of using a laminate including a temporary fixing layer provided with a thermally expandable adhesive layer containing thermally expandable particles and a thermosetting resin layer has been studied. That is, a placing step and a coating step of placing a semiconductor chip on the thermosetting resin layer included in the laminate are carried out, and thereafter, the thermosetting resin layer and the sealing material are thermally cured to obtain a laminate with a cured resin layer. After the sealing body is hardened, the heat-expandable particles are foamed to separate the hardened sealing body with the cured resin layer from the temporary fixing layer. According to this method, since the hardened resin layer functions as a deformation-resistant layer of the hardened sealing body, it is possible to obtain a hardened sealing body in which deformation is suppressed.

On the other hand, when according to the above method, any one of the treatment of making the thermally expandable particles foam and the treatment of hardening the thermosetting resin layer is heat treatment, so the heat treatment of making the thermosetting resin layer harden In this method, the heat-expandable particles in the temporarily fixed layer may foam. According to the research results of the inventors of the present invention, before the thermosetting resin layer is fully cured, if the thermally expandable particles in the temporarily fixed layer are foamed, the detachability of the temporarily fixed layer will be deteriorated in the subsequent separation step. There are deteriorating conditions. Therefore, it is highly expected to have a method that can be applied to supply the hardened resin layer of the anti-deformation layer to the hardened sealing body, and after forming the hardened sealed body with the hardened resin layer, the hardened resin layer can be easily separated from the temporary fixing layer to produce a hardened seal. body laminates.

In view of the above-mentioned problems, the present invention proposes a support layer and a hardening resin layer, which can fix the object to be sealed on the surface of the hardening resin layer and perform sealing work, and also provide a sealant for the sealing work. The cured resin layer of the anti-warping layer of the cured sealing body formed, and the laminated body in which the cured resin layer and the aforementioned support layer can be easily separated, and the production method of the cured sealed body using the laminated body are aimed at. [The way to solve the problem]

The inventors of the present invention, as a result of intensive research on solving the above-mentioned problems, found that the above-mentioned problems can be solved by the following invention, and thus completed the present invention. That is, the present invention relates to the following [1] to [11]. [1] A laminate characterized by having an energy ray-curable resin layer (I), and a support layer (II) supporting the energy ray-curable resin layer (I); the energy ray-curable resin layer (I), To have an adhesive surface, the support layer (II) has a base material (Y) and an adhesive layer (X), at least one of the base material (Y) and the adhesive layer (X) contains heat-expandable particles , The cured resin layer (I') formed by curing the energy ray curable resin layer (I) and the support layer (II) are separated at the interface through the treatment of expanding the thermally expandable particles. [2] The laminate according to the above [1], wherein the storage elastic modulus E' at 23°C of the cured resin layer (I') formed by curing the energy ray curable resin layer (I) is 1.0×10 ⁷ ~1.0×10 ¹³ Pa. [3] The laminate according to the above [1] or [2], wherein the thickness of the energy ray curable resin layer (I) is 1 to 500 μm. [4] The laminate according to any one of the above [1] to [3], wherein the visible light transmittance of the energy ray curable resin layer (I) is 5% or more. [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 (X) is a non-expandable adhesive layer. [7] The laminate according to the above [5] or [6], wherein the adhesive layer (X) and the energy ray curable resin layer (I) are directly laminated. [8] The laminate according to any one of the above [5] to [7], wherein the base material (Y) has a non-expandable base material layer (Y2) and an expandable base material layer (Y1), and supports Layer (II) has a non-expandable base material layer (Y2), an expandable base material layer (Y1), and an adhesive layer (X) in this order. The adhesive layer (X) and the energy ray curable resin layer (I) for direct lamination. [9] The laminate according to any one of the above [1] to [8], which is used to form a cured sealing body containing the object to be sealed, and is composed of the energy ray curable resin layer (I). Place the object to be sealed on a part of the surface, and irradiate the energy ray curable resin layer (I) with energy rays to form a cured resin layer (I') formed by curing the energy ray curable resin layer (I). The object to be sealed, and at least the surface of the cured resin layer (I') on the peripheral part of the object to be sealed are covered with a thermosetting sealing material, and after the sealing material is thermally cured, the aforementioned heat-expandable particles are treated to expand, The cured resin layer (I') and the support layer (II) are separated at the interface. [10] The laminate described in [9] above, which is used to prevent warpage of the hardened sealing body. [11] A method for producing a cured sealing body, which is a method of producing a cured sealing body using the laminate described in any one of the above [1] to [10], characterized by comprising the following steps (i) to ( iv): Step (i): A step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the above-mentioned laminate. Step (ii): Irradiating energy ray with energy ray and curing Resin layer (I), the step of forming a cured resin layer (I') formed by curing the energy ray curable resin layer (I) Step (iii): On the aforementioned sealing object, at least the peripheral portion of the sealing object The surface of the cured resin layer (I') is coated with a thermosetting sealing material, and the sealing material is thermally cured to form a hardened sealing body comprising the aforementioned object to be sealed. Step (iv): by making the aforementioned thermally expandable The particle expansion treatment is a step of making the hardened resin layer (I') and the support layer (II) separate at the interface to obtain a hardened sealing body with a hardened resin layer. [Effect of Invention]

The content of the present invention is to provide a support layer and a hardening resin layer, which can fix the object to be sealed on the surface of the hardening resin layer and carry out the sealing process, and also provide the product formed by the sealing process. A cured resin layer of a warpage-resistant layer of a hardened sealing body, a laminate capable of easily separating the hardened resin layer from the support layer, and a method for producing a cured sealed body using the laminated body.

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 above-mentioned layer after treatment-volume of the above-mentioned layer before treatment)/volume of the above-mentioned layer before treatment}×100 Also, "expansion treatment" is, for example, to include thermal expansion In the case of a layer of thermally expandable particles, heat treatment for 3 minutes may be performed at the expansion initiation temperature (t) of the thermally expandable particles.

In this specification, the term "active ingredient" means, among the components contained in the target composition, the diluent solvent is excluded.

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".

The components and materials exemplified in this specification can be used alone or in combination of two or more without special limitations. In the case of using two or more in combination, the combination and ratio of these can be adjusted. Make any choice.

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 that it has the property of being cured by irradiation with energy rays, and "non-energy ray curable" means that it has the property of being cured by irradiating energy rays.

[Laminate] A laminate according to an aspect of the present invention has an energy ray-curable resin layer (I) and a support layer (II) supporting the energy ray-curable resin layer (I). The energy ray curable resin layer (I) has an adhesive surface. The support layer (II) has a base material (Y) and an adhesive layer (X), and at least one of the base material (Y) and the adhesive layer (X) contains thermally expandable particles.

In the laminate of one aspect of the present invention, the heat-expandable particles in the support layer (II) are subjected to expansion treatment, and the cured resin layer (I') formed by curing the energy ray-curable resin layer (I) can be combined with the The support layer (II) is separated at its interface. That is, in the laminated body of one aspect of the present invention, the heat-expandable particles are expanded through heat-expansion treatment, and irregularities are generated on the surface of the layer containing the heat-expandable particles, thereby reducing the support layer (II) and the energy ray hardening property. The contact area of the cured resin layer (I') formed by curing the resin layer (I). As a result, the interface between 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 one aspect of the present invention, since heat treatment is not required when the energy ray-curable resin layer (I) is cured, when the energy ray-curable resin layer (I) is cured, the supporting The heat-expandable particles in the layer (II) do not expand, but can make the cured resin layer (I') formed by curing the support layer (II) and the energy ray curable resin layer (I) have excellent separability .

A laminated body according to an aspect of the present invention is a method suitable for forming a hardened sealing body including the aforementioned object to be sealed. The object is irradiated with the energy ray curable resin layer (I) to form a cured resin layer (I') formed by hardening the energy ray curable resin layer (I), and the aforementioned sealed object and the sealed object The surface of the hardened resin layer (I') at least in the peripheral part of the object is covered with a thermosetting sealing material. After the sealing material is thermosetted, the aforementioned heat-expandable particles are expanded to make the hardened resin layer (I') It is separated from the support layer (II) at this interface. The hardened sealing body formed by the above method has a hardened resin layer (I') on the side where the proportion of semiconductor wafers is relatively high. As a result, it is presumed that the difference in shrinkage stress between the two surfaces of the hardened sealing body can be reduced to obtain a hardened sealing body that can effectively suppress deformation. That is, the laminated body of one aspect of the present invention is suitable as a warpage-resistant laminated body for anti-warping of a hardened sealing body. In this case, the laminated body of one aspect of the present invention has the energy ray-curable resin layer (I) whose adhesive force can be adjusted more easily than the thermosetting resin layer, so that the object to be sealed can be sealed more reliably. part of the surface. In addition, when the thermosetting resin layer is heated at a high temperature, it will soften mainly in the initial stage of curing, and easily cause the possibility of wafer displacement. The energy ray-curable adhesive composition is It will be hardened by the irradiation of energy rays without softening, so it can avoid the wafer shift phenomenon that occurs during the hardening process.

<Configuration of Laminate> Next, the configuration of a laminate according to an aspect of the present invention will be described with reference to the drawings. Figures 1 to 3 are cross-sectional schematic diagrams of laminates showing the constitution of the laminates of the first to third aspects of the present invention. In addition, in the following laminates of the first aspect to the third aspect of the present invention, the adhesive surface (that is, The surface on the opposite side to the support body) and the surface on the opposite side to the support layer (II) side of the energy ray curable resin layer (I) may further have a structure in which a laminate release material is laminated.

[Laminated body of the first aspect] The laminated body of the first aspect of the present invention is, for example, the laminated body 1a, 1b shown in FIG. 1 . The laminates 1a and 1b are provided with an energy ray curable resin layer (I), and a support layer (II) having a base material (Y) and an adhesive layer (X), and have the base material (Y) and the energy A configuration in which the linear curable resin layer (I) is directly laminated. In addition, in the laminated body of the first aspect of the present invention, the adhesive surface of the adhesive layer (X) is attached to a support (not shown in the drawings).

The support layer (II) is one that contains heat-expandable particles in at least one layer, and in the laminate 1a, the base material (Y) is constituted only by a single layer of the expandable base material layer (Y1) containing heat-expandable particles Substrate. The base material (Y), like the laminate 1a shown in Figure 1(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 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). When the base material (Y) has an expandable base material layer (Y1) and a non-expandable base material layer (Y2), the base material (Y) can be composed of only the expandable base material layer (Y1) and the non-expandable base material layer (Y2) constituted. In addition, it is preferable to have a structure in which the expandable base material layer (Y1) and the non-expandable base material layer (Y2) are directly laminated.

The laminated body 1a shown in Figure 1(a) undergoes heat expansion treatment to expand the thermally expandable particles contained in the expandable base material layer (Y1) to form unevenness on the surface of the base material (Y), thereby reducing the The contact area of the energy ray curable resin layer (I) and the previously cured cured resin layer (I′). At this time, the adhesive surface of the adhesive layer (X) is attached to the support not shown in the drawing. The adhesive layer (X) and the support are attached in a very close manner, so even if a force that causes unevenness occurs on the surface of the expandable base material layer (Y1) on the adhesive layer (X) side, the adhesive will not Layer (X) is also prone to generate countervailing forces. Therefore, it becomes difficult to form unevenness|corrugation on the surface of the adhesive layer (X) side of a base material (Y). As a result, in the laminated body 1a, at the interface P between the base material (Y) of the support layer (II) and the hardened resin layer (I'), the entirety can be easily separated with a little force. Also, since the adhesive layer (X) of the laminated body 1a is formed of an adhesive composition having high adhesive force to the support, separation can be easily formed on the 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 (X), like the laminate 1b shown in FIG. Y1) and non-expandable substrate layer (Y2) are preferred. The stress generated by the expansion of the thermally expandable particles in the expandable base material layer (Y1) is difficult to be transmitted to the adhesive layer (X) because it is suppressed by the non-expandable base material layer (Y2). Therefore, unevenness is not easily formed on the surface of the support body side of the adhesive layer (X), and the adhesion between the adhesive layer (X) and the support body hardly changes before and after thermal expansion treatment, and can maintain good Adhesion. In this way, unevenness is more easily formed on the surface of the expandable base material layer (Y1) on the energy ray-curable resin layer (I) side, and as a result, the expandable base material layer (Y1) of the support layer (II) and the cured resin The interface P of the layer (I') can be easily separated as a whole as long as a little force is used. Also, like the laminated body 1b shown in Figure 1(b), the expandable base material layer (Y1) and the energy ray curable resin layer (I) are directly laminated, and have a non-expandable base material layer (Y2 ) is preferably formed by laminating an adhesive layer (X) on the surface opposite to the expandable substrate layer (Y1).

[Laminated body of the second aspect] The laminated body of the second aspect of the present invention includes, for example, the laminated bodies 2a and 2b shown in FIG. 2 . In the laminated body 2a, 2b, the adhesive layer (X) which the support layer (II) has has the 1st adhesive layer (X1) and the 2nd adhesive layer (X2), and has the 1st adhesive layer (X1) and the second adhesive layer (X2) sandwich the substrate (Y), and the adhesive surface of the first adhesive layer (X1) is directly laminated with the energy ray curable resin layer (I). In addition, in the laminated body of the second aspect of the present invention, the adhesive surface of the second adhesive layer (X2) is attached to a support (not shown in the drawings).

In the laminate of the second aspect of the present invention, 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 a laminate that can maintain good adhesion between the second adhesive layer (X2) and the support before and after thermal expansion treatment, as shown in Figure 2(b), the substrate ( Y) preferably has an expandable base material layer (Y1) and a non-expandable base material layer (Y2). Also, in the laminated body of the second aspect, when using the base material (Y) having the expandable base material layer (Y1) and the non-expandable base material layer (Y2), as shown in FIG. 2( b ), The first adhesive layer (X1) is laminated on the surface of the energy ray curable resin layer (I) side of the expandable base material layer (Y1), and the expandable base layer with the non-expandable base material layer (Y2) The material layer (Y1) is preferably formed by laminating the second adhesive layer (X2) on the opposite surface.

In the laminated body of the second aspect, the heat-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. Then, because of the unevenness generated on the surface of the expandable base material layer (Y1), it is pressed onto the first adhesive layer (X1), so that the adhesive surface of the first adhesive layer (X1) also forms unevenness. The process can reduce the contact area between the first adhesive layer (X1) and the hardened resin layer (I') obtained by hardening the energy ray curable resin layer (I) in advance. As a result, the interface P between the first adhesive layer (X1) and the cured resin layer (I') of the support layer (II) can be easily separated as a whole with only a little force. In addition, the laminated body of the second aspect of the present invention is a laminated body that can be easily separated as a whole with only a little force on the interface P. The base material (Y) included in the support layer (II) It is preferable that the expandable base material layer (Y1) and the first adhesive layer (X1) have a structure of direct lamination.

[Laminated body of the third aspect] The laminated body of the third aspect of the present invention includes, for example, the laminated body 3 shown in FIG. 3 . The laminate 3 shown in FIG. 3 has a first adhesive layer (X1) having an expandable adhesive layer containing heat-expandable particles on the surface side of one side of the substrate (Y), and on the substrate (Y). The surface side of the other side of Y) is equipped with a support layer (II) having a second adhesive layer (X2) having a non-expandable adhesive layer, and the first adhesive layer (X1) and the energy ray curable resin Layer (I) is a direct laminated composition. In the laminated body 3, the adhesive surface of the second adhesive layer (X2) is attached to the support (not shown in the drawing). Also, the substrate (Y) included in the laminated body of the third aspect of the present invention is preferably composed of a non-expandable substrate layer.

In the laminated body of the third aspect of the present invention, the heat-expandable particles in the first adhesive layer (X1) of the expandable adhesive layer can be expanded through thermal expansion treatment, and the heat-expandable particles in the first adhesive layer (X1) can be expanded. Asperities are generated on the surface, and the contact area between the first adhesive layer (X1) and the cured resin layer (I') obtained by curing the energy ray curable resin layer (I) in advance is reduced. On the other hand, since the substrate (Y) is laminated on the surface of the first adhesive layer (X1) on the substrate (Y) side, it is difficult to generate unevenness. Therefore, during thermal expansion treatment, irregularities can be easily formed on the surface of the first adhesive layer (X1) on the energy ray curable resin layer (I) side, and as a result, the first adhesive layer of the support layer (II) The interface P between (X1) and the cured resin layer (I') can be easily separated as a whole with only a little force.

A laminate according to an aspect of the present invention may be composed only of the support layer (II) and the energy ray-curable resin layer (I), and may have the support layer (II) and the energy ray-curable resin layer (I) Layers other than those can also be used. Examples of other layers include, for example, an adhesive layer provided on the side opposite to the support layer (II) of the energy ray curable resin layer (I). Also, the laminated body of one aspect of the present invention is preferably one that does not have a thermosetting resin layer from the viewpoint of eliminating the need for extreme heating in steps other than the thermal expansion treatment. However, the thermosetting resin layer here means a layer that is thermosetting and not energy ray curable.

<Physical properties of the laminate> (Peel force (F ₀ )) Before the hardening of the energy ray curable resin layer (I) and before the thermal expansion treatment, the object to be sealed can be sufficiently fixed without causing damage to the sealing work. From the viewpoint of adverse effects, the higher the adhesion between the support layer (II) and the energy ray curable resin layer (I), the better. Based on the above point of view, in the laminated body of an aspect of the present invention, the energy ray curable resin layer (I) is bonded between the support layer (II) and the energy ray curable resin layer (I) before being cured and before thermal expansion treatment. The peel force (F ₀ ) when separation is formed on the interface P of ) is preferably at least 100mN/25mm, more preferably at least 130mN/25mm, particularly preferably at least 160mN/25mm, and preferably at least 50000mN/25mm . 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 adhesive tape (manufactured by Linde Co., Ltd., product name "PL- SHIN") is attached to the surface of the energy ray curable resin layer (I). Then, the support layer (II) side of the laminate was attached to a glass plate (manufactured by U-KOU Shokai Co., Ltd., float glass, 3 mm (JIS R 3202 product)) via an adhesive. 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"). Then, the adhesive tape and the support layer (II) were fixed with the upper fixture of the universal tensile testing machine in such a way that the interface P between the support layer (II) and the energy ray curable resin layer (I) of the laminate was peeled off. Then, under the same environment as above, based on JIS Z 0237:2000, the peeling force measured at the time of peeling at the interface P using the 180˚ tensile peeling method at a tensile speed of 300mm/min is set to " Peel Force (F ₀ )".

(Peel force (F ₁ )) In the laminated body according to one aspect of the present invention, after the energy ray curable resin layer (I) is cured to form the cured resin layer (I'), heat expansion treatment is performed on the support layer. (II) The peeling force (F ₁ ) when separating from the interface P of the cured resin layer (I') is usually 2000mN/25mm or less in view of the fact that the interface P can be easily separated as a whole with only a little force, Preferably it is less than 1000mN/25mm, more preferably less than 500mN/25mm, more preferably less than 150mN/25mm, most preferably less than 100mN/25mm, most preferably less than 50mN/25mm, most preferably less than 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 )> After the laminate was left to stand at 23°C and 50%RH (relative humidity) for 24 hours, the adhesive tape (manufactured by Linde Co., Ltd., product name "PL- SHIN") is attached to the surface of the energy ray curable resin layer (I) of the laminate. Then, the support layer (II) side of the laminate was attached to a glass plate (manufactured by U-KOU Shokai Co., Ltd., float glass, 3 mm (JIS R 3202 product)) via an adhesive. Next, ultraviolet rays were irradiated three times under conditions of illuminance 215 mW/cm ² and light intensity 187 mJ/cm ² to harden the energy ray curable resin layer (I) to form a cured resin layer (I′). Subsequently, the glass plate and the laminate were heated at the maximum expansion temperature for 3 minutes to expand the heat-expandable particles in the expandable substrate layer (Y1) of the laminate. Thereafter, in the same manner as the measurement of the above-mentioned peeling force (F ₀ ), under the same conditions, the peeling force measured when the interface P of the support layer (II) and the cured resin layer (I') is peeled off is set to "Peel force (F ₁ )". In addition, in the measurement of the peeling force (F ₁ ), the hardened resin layer (I') can be completely separated on the interface P when the support layer (II) of the laminate is fixed using the upper grip of the universal tensile testing machine. , but if there is no fixation, the measurement ends, and the peeling force (F ₁ ) at this time is "0mN/25mm".

(Adhesive Force of Adhesive Layer (X)) In the laminate of one aspect of the present invention, at room temperature (23°C), the adhesive layer (X) (first adhesive) of the support layer (II) layer (X1) and the second adhesive layer (X2)), preferably 0.1-10.0N/25mm, more preferably 0.2-8.0N/25mm, particularly preferably 0.4-6.0N/25mm, most preferably It is 0.5~4.0N/25mm. When the supporting layer (II) has the first adhesive layer (X1) and the second adhesive layer (X2), the adhesive force of the first adhesive layer (X1) and the second adhesive layer (X2) are respectively in the above range It is better, but from the point of view of improving the adhesion with the support and easily forming a whole separation at the interface P, the adhesive force of the second adhesive layer (X2) attached to the support should be higher than that of the first adhesive The layer (X1) with higher adhesion is preferred.

(Adhesion of the energy ray-curable resin layer (I)) In the laminated body of an aspect of the present invention, the energy ray-curable resin layer (I) is mounted and sealed from the viewpoint of good adhesion to the object to be sealed. The surface on the object side (that is, the surface opposite to the support layer (II)) has adhesiveness. Specifically, at room temperature (23° C.), the adhesive force of the energy ray curable resin layer (I) on the surface on which the object to be sealed is placed is preferably 0.05 from the viewpoint that the object to be sealed can be sufficiently fixed. N/25mm or more, more preferably 0.10N/25mm or more, particularly preferably 0.50N/25mm or more. The upper limit of the adhesive force on the above surface is not particularly limited, but it is usually 50N/25mm or less, and may be 40N/25mm or less, 30N/25mm or less.

In addition, in this specification, the adhesive force of these is the value measured by the following measuring method. <Measurement of Adhesive Strength> A PET film (manufactured by Toyobo Co., Ltd., product name "COSMO") with a thickness of 50 μm was laminated on the surface of the adhesive layer (X) or the energy ray-curable resin layer (I) formed on the release film. -SHUNE A4100"). Then, attach the surface of the adhesive layer (X) or the energy ray-curable resin layer (I) to a stainless steel plate (SUS304 360-degree grinding) of the adherend, and place it at 23°C, 50%RH (relative humidity) Under the environment, after standing for 24 hours, in the same environment, according to JIS Z 0237: 2000, use the 180˚ tensile peeling method and the tensile speed of 300mm/min to measure its adhesion at 23°C .

(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 is 50mN/5mmφ for the surface of the target base material , then it is judged that the substrate is "non-adhesive substrate". In addition, 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 tensile strength on the surface of the substrate (Y) used in the support layer (II) used in one aspect of the present invention is usually less than 50mN/5mmφ, preferably less than 30mN/5mmφ, more preferably It is less than 10mN/5mmφ, especially preferably 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 base material 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. Under the environment of 23°C and 50%RH (relative humidity), the surface of the test sample was measured according to JIS Z0237:1991 using a viscosity tester (manufactured by Nippon Special Sekki Co., Ltd., product name "NTS-4800") 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.

Subsequently, the content of each layer constituting the laminated body of one aspect of the present invention will be explained.

<Support layer (II)> The support layer (II) included in the laminated body of one aspect of the present invention has a substrate (Y) and an adhesive layer (X), and the substrate (Y) and adhesive At least one of the layers (X) contains heat-expandable particles. As described above, the support layer (II) is a layer separated from the energy ray-curable resin layer (I) of the object to be supported by thermal expansion treatment, and is a layer that functions as a temporary fixing layer. A layer containing heat-expandable particles is included in the composition of the base material (Y) and in the case of the composition of the adhesive layer (X). The support layer (II) used in one aspect of the present invention ) can be divided into the following forms.・Support layer (II) of the first aspect: A support layer (II) having a base material (Y) having an expandable base material layer (Y1) containing heat-expandable particles.・Support layer (II) of the second aspect: On both sides of the substrate (Y), there is a first adhesive layer (X1) containing an expandable adhesive layer as heat-expandable particles as a non-expandable adhesive The support layer (II) of the second adhesive layer (X2) of the layer.

[Support layer (II) of the first aspect] The support layer (II) of the first aspect, as shown in Figures 1-2, the substrate (Y) is an expandable substrate layer containing thermally expandable particles ( Y1). In the support layer (II) of the first aspect, the interface P can be easily separated as a whole with only a little force, and the adhesive layer (X) is preferably a non-expandable adhesive layer. Specifically, in the support layer (II) of the laminates 1a and 1b shown in Fig. 1, the adhesive layer (X) is preferably a non-expandable adhesive layer. In addition, in the supporting layer (II) of the laminates 2a and 2b shown in FIG. 2, either the first adhesive layer (X1) or the second adhesive layer (X2) is non-expandable adhesive. Agent layer is better. As shown in the support layer (II) of the first aspect, since the base material (Y) has an expandable base material layer (Y1), the adhesive layer (X) does not need to have expandability, and does not need to be subject to the expansion-imparting condition. Constrained by composition, composition and manufacturing process. In this way, when designing the adhesive layer (X), for example, performance such as adhesiveness, productivity, economical efficiency, etc., can be designed with priority for expected performance other than swelling, and the adhesive layer (X) can be improved. ) degrees of design freedom.

The thickness of the substrate (Y) before thermal expansion treatment of the support layer (II) of the first aspect is preferably 10-1000 μm, more preferably 20-700 μm, particularly preferably 25-500 μm, most preferably 30-30 μm. 300 μm.

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

Also, in this specification, for example, as shown in FIG. 2, when the support layer (II) has a plurality of adhesive layers (X), the above-mentioned "thickness of the adhesive layer (X)" means that each adhesive layer The thickness (in FIG. 2, the respective thicknesses of the first adhesive layer (X1) and the second adhesive layer (X2)) means. In addition, in this specification, the thickness of each layer constituting the laminate means the value measured by the method described in the examples.

In the support layer (II) of the first aspect, the thickness ratio [(Y1)/(X)] of the expandable base material layer (Y1) before the thermal expansion treatment to the adhesive layer (X) is preferably Below 1000, more preferably below 200, particularly preferably below 60, most preferably below 30. When the thickness ratio is less than 1000, after thermal expansion treatment, a laminate can be formed at the interface P between the support layer (II) and the hardened resin layer (I’), which can be easily separated as a whole with a little force. Moreover, 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 support layer (II) of the first aspect, the base material (Y), as shown in Figure 1(a), may be composed only of the expandable base material layer (Y1), as shown in Figure 1( As shown in b), one may have an expandable base material layer (Y1) on the side of the energy ray curable resin layer (I) and a non-expandable base material layer (Y2) on the side of the adhesive layer (X).

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

[Support layer (II) of the second aspect] The support layer (II) of the second aspect, as shown in FIG. The first adhesive layer (X1) which is a non-expandable adhesive layer, and the second adhesive layer (X2) which is a non-expandable adhesive layer. Also, in the support layer (II) of the second aspect, the first adhesive layer (X1) as the expandable adhesive layer is in direct contact with the energy ray curable resin layer (I). In the support layer (II) of the second aspect, the base material (Y) is preferably a non-expandable base material. The non-expandable base material is preferably composed of only the non-expandable base material layer (Y2).

In the support layer (II) of the second aspect, the first adhesive layer (X1) as an expandable adhesive layer before heat expansion treatment, and the second adhesive layer (X2) as a non-expandable adhesive layer The thickness ratio [(X1)/(X2)] is preferably 0.1-80, more preferably 0.3-50, particularly preferably 0.5-15.

In addition, the thickness ratio of the first adhesive layer (X1) as an expandable adhesive layer before the thermal expansion treatment of the support layer (II) of the second aspect to the substrate (Y) is [(X1)/(Y )], preferably 0.05-20, more preferably 0.1-10, particularly preferably 0.2-3.

Hereinafter, the thermally expandable particles contained in any layer constituting the support layer (II) will be described, and the expandable substrate layer (Y1) and the non-expandable substrate layer (Y2) constituting the substrate (Y) will be described in detail. , and the adhesive layer (X).

[Heat-expandable particles] The heat-expandable particles used in one aspect of the present invention may be any particles that can be expanded by a specific thermal expansion treatment. The average particle diameter of the heat-expandable particles used in one aspect of the present invention before expansion at 23°C is preferably 3-100 μm, more preferably 4-70 μm, particularly preferably 6-60 μm, and most preferably 10-100 μm. 50 μm. Also, the average particle diameter before expansion of the heat-expandable particles refers to the volume median particle diameter (D ₅₀ ), measured using a laser diffraction particle size distribution analyzer (for example, manufactured by Malvern, product name "MASTERSIZER 3000") In the obtained particle distribution of the heat-expandable particles before expansion, the cumulative volume frequency calculated from the side where the particle diameter of the heat-expandable particles before expansion is smaller corresponds to 50% of the particle diameter.

The 90% particle size (D ₉₀ ) of the heat-expandable particles used in one aspect of the present invention before expansion at 23°C is preferably 10-150 μm, more preferably 20-100 μm, particularly preferably 25-90 μm, The optimum is 30-80 μm. Also, 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 that the cumulative volume frequency calculated from the side where the particle size of thermally expandable particles before expansion is smaller is equivalent to 90% of the particle size.

The thermally expandable particles used in one aspect of the present invention should 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 whose expansion initiation temperature (t) is adjusted to 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 initiation temperature (t) of heat-expandable particles refers to the value measured according to the method described in the examples.

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

Included components contained within 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, cyclo Tridecane, Hexylcyclohexane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Heptadecane, Octadecane, Nonadecane, Isotridecane, 4-Methyldodecane, Isotetradecane, Isopentadecane, Isohexadecane, 2,2,4,4,6,8,8-Heptamethylnonane, Isoheptadecane, Isooctadecane, Isnonadecane, 2,6,10,14-Tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane , pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. These internal components can be used alone or in combination of two or more. The expansion initiation temperature (t) of heat-expandable particles can be adjusted by properly selecting the type of inner package components.

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 material layer (Y1)> When 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 undergoes specific thermal expansion treatment , can produce a dilated 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 radiation treatment, etc., embossing 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 of the energy ray-curable resin layer (I) on which the layer (I) is laminated must be easily formed into a concave-convex state. 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 the energy rays can be combined with the curable resin layer (I ) on the surface of the support layer (II) on the laminated side is more likely to form unevenness. As a result, a laminate 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, the flow of the thermally expandable particles after expansion can be suppressed, and the maintenance of the uneven shape on the surface of the support layer (II) laminated on the side of the energy ray curable resin layer (I) can be improved. 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 that does not impair the effect of the present invention.  Additives for substrates, such as light stabilizers, antioxidants, antistatic agents, slip agents, anti-adhesive agents, colorants, etc. In addition, these additives for base materials may be used alone or in combination of two or more. When these base material additives are contained, the content of the respective base material additives 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 aforementioned resin.

The content of the thermally expandable particles is preferably 1 to 40% by mass relative to the total amount (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, it is 5-35 mass %, It is especially preferable that it is 10-30 mass %, Most preferably, it is 15-25 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 this 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, more preferably It is preferably 60 to 95% by mass, particularly preferably 65 to 90% by mass, most preferably 70 to 85% by 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-based resin is preferably the following resin (U1).・Urethane prepolymer (UP), a urethane acrylate resin (U1) obtained by polymerizing a vinyl compound containing (meth)acrylate.

(Urethane-based resin (U1)) Urethane prepolymer (UP) as the main chain of urethane-based resin (U1), for example, a reaction product of polyalcohol and polyvalent isocyanate wait. In addition, the urethane prepolymer (UP) is preferably obtained by 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 in combination of two or more. 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 such as 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 in combination of two or more.

The content of (meth)acrylate in the vinyl compound is preferably from 40 to 100% by mass, more preferably from 65 to 100% by mass, particularly preferably from 80 to 100% by mass, based on the total amount (100% by 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, and most preferably 30/70- 60/40, the best is 35/65~55/45.

(Olefin-based resin) Among the resins contained in the resin composition (y), a preferable olefin-based resin is, for example, a polymer having at least a structural unit derived from an olefin monomer. The above-mentioned olefin monomers are preferably α-olefins with 2 to 8 carbon atoms, specifically, vinyl, propenyl, butenyl, isobutenyl, 1-hexenyl, etc. Among these, vinyl and acrylic are preferred.

Specifically, olefin-based resins, such as ultra-low-density polyethylene (VLDPE, density: 880 kg/m ³ or more, less than 910 kg/m ³ ), low-density polyethylene (LDPE, density: 910 kg/m ³ or more, less than 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. In addition, the unsaturated carboxylic acid or its anhydride may be used alone or in combination of two or more.

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 number of carbon atoms in the alkyl group of the above-mentioned alkyl (meth)acrylate is preferably 1-20, more preferably 1-16, particularly preferably 1-12. The above-mentioned 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 urethane-based resins and Resins other than olefin resins. 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, for example, an oligomerized A solvent-free resin composition (y1) without adding a solvent obtained by blending an energy ray polymerizable monomer and the above-mentioned heat-expandable particles. 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 a coating film formed of a solvent-free resin composition (y1) is irradiated with energy rays, an expandable base material layer (Y1) satisfying the above requirement (1) will be easily formed.

In addition, the kind, shape, and addition amount (content) of the thermally expandable particles added to the non-solvent type resin composition (y1) are as above.

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 2,000 to 40,000, most preferably 3,000 to 35,000, most preferably 4000~30000.

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 in the resin contained in the above-mentioned resin composition (y), and the above-mentioned urethane Prepolymers (UP) are preferred. In addition, as the oligomer, a denatured olefin-based resin having an ethylenically unsaturated group can also be used.

In the solvent-free resin composition (y1), the total content of the aforementioned oligomers and energy ray polymerizable monomers is preferably from 50 to 99% by mass, more preferably 60-95% by mass, particularly preferably 65-90% by mass, most preferably 70-85% 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 included, the hardening reaction can proceed sufficiently even when irradiated with low-energy energy rays.

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 in combination of two or more.

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., which can be combined with one aspect of the present invention Make appropriate choices for the use of the laminated body.

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. Non-expandable substrate layer (Y2) that is made of two or more forming materials, for example, paper laminated with thermoplastic resin such as polyethylene, resin film or sheet surface containing resin with metal film, etc. 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.

Among them, in one aspect of the present invention, when the expandable particles contained in the expandable base material layer (Y1) expand, the non-expandable base material layer (Y2) of the expandable base material layer (Y1) can be suppressed From the viewpoint of forming unevenness on the surface of the expandable base material layer (Y1) on the side of the adhesive layer (X1), etc., the non-expandable base material layer (Y2) has a Rigidity to the extent that the flexible particles expand and deform is preferred. Specifically, the storage elastic modulus E'(t) of the non-expandable base material layer (Y2) at the temperature (t) at which the expandable particles start to expand is preferably 1.1×10 ⁷ Pa or more.

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-adhesion treatment, or primer treatment by oxidation, embossing, or the like in the same manner as the above-mentioned expandable base material layer (Y1).

Moreover, when the non-expandable base material layer (Y2) contains resin, it may contain resin composition (y) simultaneously with this resin, and may contain the above-mentioned additive for base material.

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 by the above formula is less than 5%, preferably less than 2%, more preferably less than 1%, and most preferably less than 1%. Up to 0.1%, the best is less than 0.01%.

Moreover, in a non-expandable base material layer (Y2), when this volume change rate exists in the said range, you may contain thermally expandable particle|grains. 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 them, the non-expandable substrate layer (Y2) is preferably one that does not contain heat-expandable particles. When the non-expandable base material layer (Y2) contains heat-expandable particles, the less the content, the better. The specific content of heat-expandable particles is relative to the total amount (100% by mass) of the non-expandable base material layer (Y2). , 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 (X)> The adhesive layer (X) included in the support layer (II) used in one aspect of the present invention can be formed of an adhesive composition (x) containing an adhesive resin. In addition, the adhesive composition (x) may contain adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, if necessary. Below, each component contained in the adhesive composition (x) will be explained. Also, when the support layer (II) has the first adhesive layer (X1) and the second adhesive layer (X2), the first adhesive layer (X1) and the second adhesive layer (X2) can also be formed by The adhesive composition (x) containing each component shown below was formed.

(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 in combination of two or more. 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, when using the support layer (II) having the first adhesive layer (X1) and the second adhesive layer (X2), the first adhesive layer (X1) in contact with the energy ray curable resin layer (I) Since the acrylic resin is contained in the adhesive agent layer (X1), unevenness can be easily formed on the surface of the first adhesive layer (X1).

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 (x) or the adhesive layer (X). %, more preferably 50-100% by mass, particularly preferably 70-100% by mass, most preferably 85-100% by mass.

The content of the adhesive resin is preferably 35 to 100% by mass, more preferably It is preferably 50-100% by mass, particularly preferably 60-98% by mass, most preferably 70-95% by mass.

(Crosslinking agent) In one aspect of the present invention, when the adhesive composition (x) contains an adhesive resin having a functional group, it preferably further contains a crosslinking agent. The cross-linking agent is capable of reacting with the adhesive resin having a functional group, and using the functional group as the starting point of cross-linking to form cross-linking 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 preferred 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 (x) 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 400-9000, more preferably 500-8000, and most preferably 800-5000.

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 the tackifier refers to the value measured based on JIS K 2531. Tackifiers can be used alone or in combination of two or more different in softening point and structure. In addition, when two or more plural tackifiers are used, the weighted average of the softening points of these plural tackifiers is preferably within the above 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 (x) or the total amount (100% by mass) of the adhesive layer (X), and 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.

(Additives for Adhesives) In one aspect of the present invention, the adhesive composition (x) may contain, in addition to the above-mentioned additives, additives for adhesives commonly used in adhesives, as long as the effect of the present invention is not impaired. .  These additives for adhesives, for example, antioxidants, softeners (plasticizers), antirust agents, pigments, dyes, retarders, reaction accelerators (catalysts), ultraviolet absorbers, antistatic agents, etc. In addition, these adhesive additives may be used alone or in combination of two or more. When these additives for adhesives are contained, the content of each additive for adhesives is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass, based on 100 parts by mass of the adhesive resin.

Also, when using the support layer (II) of the second aspect having the first adhesive layer (X1) as the expandable adhesive layer, the formation of the first adhesive layer (X1) as the expandable adhesive layer The material is formed from the above-mentioned adhesive composition (x) and an expandable adhesive composition (x11) containing heat-expandable particles. The thermally expandable particles are as described above. The content of the thermally expandable particles is preferably 1 to 70% by mass relative to the total amount (100% by mass) of the active ingredient of the expandable adhesive composition (x11) or the total amount (100% by mass) of the expandable adhesive layer, More preferably, it is 2-60 mass %, Most preferably, it is 3-50 mass %, Most preferably, it is 5-40 mass %.

On the other hand, when the adhesive layer (X) is a non-expandable adhesive layer, the adhesive composition (x) as a material for forming the non-expandable adhesive layer preferably does not contain heat-expandable particles. In the case of containing heat-expandable particles, the less the content, the better. Generally, relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X), 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 layer (II) having a first adhesive layer (X1) and a second adhesive layer (X2) as a non-expandable adhesive layer is used. At 23°C, the storage shear modulus G'(23) of the first adhesive layer (X1) as a non-expandable adhesive layer is preferably 1.0×10 ⁸ Pa or less, more preferably 5.0× 10 ⁷ Pa or less, particularly preferably 1.0×10 ⁷ Pa or less. When the storage shear elastic modulus G'(23) of the first adhesive layer (X1) which is a non-expandable adhesive layer is 1.0×10 ⁸ Pa or less, for example, the laminated body 2a, 2b etc. shown in FIG. 2 In the case of the structure, it can expand the thermally expandable particles in the expandable base material layer (Y1) through thermal expansion treatment, so that the surface of the first adhesive layer (X1) in contact with the cured resin layer (I') Easier to form bumps. 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 (X1), which is a non-expandable adhesive layer, is preferably at least 1.0×10 ⁴ Pa, more preferably 5.0× 10 ⁴ Pa or more, particularly preferably 1.0×10 ⁵ Pa or more.

The light transmittance of the supporting layer (II) in the laminate according to one aspect of the present invention at a wavelength of 375 nm 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 energy ray (ultraviolet rays) irradiates the energy ray curable resin layer (I) through the supporting layer (II), the energy ray can make the hardening degree of the curable resin layer (I) more upward promote. Also, the upper limit of the light transmittance at a wavelength of 375 nm is not particularly limited, for example, it may be 95% or less. The above-mentioned transmittance can be measured by a known method using a spectrophotometer. From the viewpoint of achieving the above-mentioned light transmittance, when the base material (Y) and the adhesive layer (X) of the support layer (II) contain a coloring agent, within the range that does not hinder the effect of the present invention, adjust its content to Good is better. When a coloring agent is contained, the less the content, the better, generally relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x) or the total amount (100% by mass) of the adhesive layer (X), 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 substrate (Y) is less than 0.01% by mass. The total amount (100% by mass) of the active ingredient of the resin composition (y) or the total amount (100% by mass) of the substrate (Y) is preferably less than 1% by mass, more preferably less than 0.1% by mass, most preferably It is less than 0.01% by mass, most preferably less than 0.001% by mass.

<Energy ray curable resin layer (I)> The energy ray curable resin layer (I) is not particularly limited as long as it can be hardened by irradiation with energy rays. (a) formed of the energy ray curable resin composition.

[Energy ray-curing component (a)] The energy ray-curing component (a) is a component that is hardened by irradiation of energy rays. The energy ray curable component (a) is, for example, a polymer (a1) having an energy ray curable double bond and having a mass average molecular weight (Mw) of 80,000 to 2,000,000 (hereinafter also referred to as "polymer (a1)"), A compound (a2) having an energy ray-curable double bond with a molecular weight of 100 to 80,000 (hereinafter also referred to simply as "compound (a2)") and the like. The energy ray-curing component (a) may be used alone or in combination of two or more.

(Polymer (a1)) The polymer (a1) is a polymer having an energy-ray-curable double bond and a mass average molecular weight (Mw) of 80,000 to 2,000,000. The polymer (a1), for example, is composed of an acrylic polymer (a11) having a functional group X capable of reacting with a group possessed by other compounds, a group Y having a group Y capable of reacting with the above-mentioned functional group X, and an energy ray An energy ray-curable compound (a12) with a curable double bond, an acrylic resin (a1-1) formed by polymerization, and the like. The polymer (a1) may be used alone or in combination of two or more.

・Acrylic polymer (a11) The functional group X of the acrylic polymer (a11) is, for example, a hydroxyl group, a carboxyl group, an amine group, or a substituted amino group (one or two of the hydrogen atoms in the amine group can be replaced by One or more selected from the group consisting of a group substituted with a group other than a hydrogen atom) and an epoxy group.

The acrylic polymer (a11), for example, is formed by copolymerizing an acrylic monomer having the above-mentioned functional group X with an acrylic monomer not having the above-mentioned functional group X, or other than these monomers, and acrylic acid Those formed by copolymerization of monomers other than acrylic monomers (non-acrylic monomers). The acrylic polymer (a11) may be a random copolymer or a block copolymer. Acrylic polymers (a11) may be used alone or in combination of two or more.

Acrylic monomers having the above-mentioned functional group X include, for example, monomers containing hydroxyl groups, monomers containing carboxyl groups, monomers containing amine groups, monomers containing substituted amino groups, monomers containing epoxy groups, and the like. Hydroxyl-containing monomers, such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; vinyl alcohol, allyl alcohol, etc. non-(meth)acrylic unsaturated alcohols (unsaturated alcohols that do not have a (meth)acryl skeleton), etc. Carboxyl-containing monomers, such as (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, maleic acid Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds) such as acid and ciconic acid; anhydrides of the above-mentioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate, etc. Among these, monomers containing hydroxyl groups and monomers containing carboxyl groups are preferred, and monomers containing hydroxyl groups are more preferred.

Acrylic monomers that do not have the above-mentioned functional group X, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth)acrylate ) tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ((meth) ) (palmyl acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. Alkyl (meth)acrylate with a chain structure of 18, etc. Also, acrylic monomers that do not have the above-mentioned functional group X, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, (methoxymethyl) (meth)acrylic acid esters containing alkoxyalkyl groups such as ethoxyethyl acrylate; Acrylates; non-crosslinkable (meth)acrylamides and their derivatives; (meth)acrylate N,N-dimethylaminoethyl, (meth)acrylate N,N-dimethyl Non-crosslinked (meth)acrylates with tertiary amino groups such as aminopropyl groups. The above-mentioned non-acrylic monomers, for example, olefins such as ethylidene and norbornene; vinyl acetate; styrene, etc.

In the acrylic polymer (a11), the content of the structural unit amount derived from the acrylic monomer having the above-mentioned functional group X is preferably 0.1 to 50% by mass, more preferably It is 1 to 40% by mass, particularly preferably 3 to 30% by mass. When content of the said structural unit is in the said range, in the obtained acrylic resin (a1-1), content of an energy-beam curable double bond can be easily adjusted to a preferable range.

・Energy ray-curable compound (a12) The energy ray-curable compound (a12) is a compound having a group Y capable of reacting with the above-mentioned functional group X and an energy ray-curable double bond. The above-mentioned group Y is, for example, one or more selected from the group consisting of isocyanate group, epoxy group and carboxyl group, and among them, isocyanate group is preferable. When the energy ray-curable compound (a12) has an isocyanate group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as the above-mentioned functional group. The number of energy ray-curable double bonds contained in the energy ray-curable compound (a12) is preferably 1 to 5, more preferably 1 to 3 in 1 molecule. The energy ray-curing compound (a12) may be used alone or in combination of two or more.

Energy ray-curing compounds (a12), for example, 2-methacryloxyethyl isocyanate, methyl-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryl isocyanate, allyl Isocyanates, 1,1-(bisacryloxymethyl)ethyl isocyanate; diisocyanate compounds or polyisocyanate compounds, acryl monoisocyanate compounds obtained by reaction with hydroxyethyl (meth)acrylate; diisocyanate compounds Or polyisocyanate compound, polyalcohol compound, and acryl monoisocyanate compound obtained by reacting with hydroxyethyl (meth)acrylate, etc. Among these, 2-methacryloxyethyl isocyanate is preferable.

In the acrylic resin (a1-1), the content of the energy ray-curable double bond generated from the energy ray-curable compound (a12) relative to the content of the above-mentioned functional group X generated from the acrylic polymer (a11) The ratio is preferably 20-120 mol%, more preferably 5-100 mol%, particularly preferably 50-100 mol%. When the above-mentioned ratio is in the above-mentioned range, the adhesive force of the cured resin layer (I') formed through curing can be further increased. In addition, when the energy ray-curable compound (a12) is a monofunctional (having one of the above-mentioned groups in one molecule) compound, the upper limit of the ratio of the above-mentioned content is 100 mol%, and the energy ray-curable compound (a12) is In the case of a polyfunctional (having two or more of the above-mentioned groups in one molecule) compound, the upper limit of the ratio of the above-mentioned content exceeds 100 mol%.

The content of the acrylic resin (a1-1) is preferably: 1 to 40% by mass, more preferably 2 to 30% by mass, particularly preferably 3 to 20% by mass.

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

At least a part of the polymer (a1) may be cross-linked by a cross-linking agent (e) described later, or may not be cross-linked.

(Compound (a2)) The compound (a2) is a compound having an energy ray hardening double bond and a molecular weight of 100 to 80,000. The energy ray-hardening double bond possessed by the compound (a2) is preferably a (meth)acryl group, a vinyl group, or the like. The compound (a2) includes, for example, a low molecular weight compound having an energy ray-curable double bond, an epoxy resin having an energy ray-curable double bond, a phenol resin having an energy ray-curable double bond, and the like. Compound (a2) may be used alone or in combination of two or more.

The aforementioned low-molecular-weight compounds with energy-ray-curable double bonds, such as polyfunctional monomers and oligomers, are preferably acrylate-based compounds with (meth)acryl groups. Acrylate-based compounds such as 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A Di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxyethoxy)benzene base] fennel, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (tricyclodecane dihydroxy Methyl di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate Alcohol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, Tripropylene glycol di(meth)acrylate, Polypropylene glycol di(meth)acrylate, Polybutylene glycol di(meth)acrylate ester, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) Acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acrylate 2-functional (meth)acrylates such as base) acryloxypropane; tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone denatured tris-(2 -(meth)acryloxyethyl)isocyanurate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri( Meth)acrylate, Di-Trimethylolpropane Tetra(meth)acrylate, Ethoxylated Pentaerythritol Tetra(meth)acrylate, Pentaerythritol Tetra(meth)acrylate, Dipentaerythritol Poly(meth)acrylate Polyfunctional (meth)acrylates such as acrylates and dipentaerythritol hexa(meth)acrylate; polyfunctional (meth)acrylate oligomers such as urethane (meth)acrylate oligomers wait.

As the above-mentioned epoxy resin having an energy ray-curable double bond and the phenol resin having an energy ray-curable double bond, for example, those described in paragraph 0043 of "JP-A-2013-194102" and the like can be used. These resins may also correspond to the resins constituting the thermosetting component (f) described later, and are treated as compound (a2) in the present invention.

The mass average molecular weight (Mw) of the compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.

The content of the compound (a2) is preferably 1 to 40% with respect to the total amount (100% by mass) of the active ingredients of the energy ray-curable resin composition or the total amount (100% by mass) of the energy ray-curable resin layer (I). % by mass, more preferably 2 to 30% by mass, particularly preferably 3 to 20% by mass.

[Polymer (b) not having an energy ray-curable double bond] When the energy ray-curable resin composition contains the compound (a2), it may further contain a polymer (b) not having an energy ray-curable double bond ( Hereinafter, it is also referred to simply as "polymer (b)"). The polymer (b) may be used alone or in combination of two or more.

Polymer (b), for example, acrylic polymer, phenoxy resin, urethane resin, polyester, rubber-based resin, urethane acrylate resin, polyvinyl alcohol (PVA), butyral resin, Polyester urethane resin, etc. Among these, an acrylic polymer (hereinafter, "acrylic polymer (b-1)") is preferable.

The acrylic polymer (b-1) may be a known component. For example, it may be a homopolymer of one type of acrylic monomer, or a copolymer of two or more types of acrylic monomers, or it may be A copolymer composed of one or more acrylic monomers and one or more monomers other than acrylic monomers (non-acrylic monomers).

Acrylic monomers constituting the acrylic polymer (b-1), for example, alkyl (meth)acrylates, (meth)acrylates having a ring skeleton, (meth)acrylates containing epoxy groups, Hydroxyl-containing (meth)acrylates, substituted amino-containing (meth)acrylates, etc. Here, the "substituted amino group" is as described above.

Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, Heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, ( Isononyl methacrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Lauryl (meth)acrylate (Lauryl (meth)acrylate), (Meth)acrylic acid Tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate ((meth)acrylic acid Palmityl), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a chain with 1 to 18 carbon atoms Structured (meth)acrylic acid alkyl esters, etc.

(Meth)acrylates having a cyclic skeleton, for example, cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; benzyl (meth)acrylate Aralkyl (meth)acrylates such as esters; cycloenyl (meth)acrylates such as dicyclopentenyl (meth)acrylates; (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylates base) cycloalkyleneoxyalkyl acrylate, etc.

(Meth)acrylates containing epoxy groups, for example, (meth)acrylic epoxy and the like. Hydroxyl-containing (meth)acrylates, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxy (meth)acrylate Hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.  (meth)acrylates containing substituted amino groups, for example, N-methylaminoethyl (meth)acrylate, etc.

Non-acrylic monomers constituting the acrylic polymer (b-1) include, for example, olefins such as vinyl and norbornene; vinyl acetate; styrene and the like.

The polymer (b) may be at least partially crosslinked by the crosslinking agent (e), or may be uncrosslinked. At least a part of the polymer (b) obtained by cross-linking with the cross-linking agent (e), for example, one obtained by reacting the reactive functional groups in the polymer (b) with the cross-linking agent (e). The above-mentioned reactive functional groups can be appropriately selected in accordance with the type of crosslinking agent (e), and are not particularly limited. For example, when the crosslinking agent (e) is a polyisocyanate compound, the reactive functional groups mentioned above are, for example, hydroxyl, carboxyl, amine, etc. Among them, hydroxyl groups with high reactivity with isocyanate groups are preferred. In addition, when the crosslinking agent (e) is an epoxy compound, the above-mentioned reactive functional groups, for example, carboxyl, amine, amido, etc., among them, the carboxyl group having high reactivity with epoxy groups better. Among them, from the viewpoint of preventing corrosion of semiconductor wafers and semiconductor wafer lines, the above-mentioned reactive functional groups are preferably groups other than carboxyl groups.

The above-mentioned polymer (b) having a reactive functional group is, for example, one obtained by polymerizing at least the above-mentioned monomer having a reactive functional group. In the case of an acrylic polymer (b-1), any one or both of the above-mentioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer can be used as the above-mentioned Reactive functional groups can be used. For example, a polymer (b) having a hydroxyl group as a reactive functional group, for example, one obtained by polymerizing a (meth)acrylate containing a hydroxyl group, etc. Among the acrylic monomers, those in which one or more hydrogen atoms are substituted by the above-mentioned reactive functional groups are obtained by polymerization.

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

The mass average molecular weight (Mw) of the polymer (b) is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000, from the viewpoint of improving the film-forming properties of the energy ray-curable resin composition.

The energy ray-curable resin composition is, for example, a composition containing either or both of the polymer (a1) and the compound (a2), and when the compound (a2) is contained, the polymer (b) is further contained. good.

The total content of the energy ray-curable component (a) and the polymer (b) is based on the total amount of active ingredients (100% by mass) of the energy ray-curable resin composition or the total amount of the energy ray-curable resin layer (I) ( 100% by mass), preferably 5 to 90% by mass, more preferably 10 to 80% by mass, particularly preferably 15 to 70% by mass. When the total content is within the above range, the energy ray hardening property can be further improved.

When energy ray curable resin composition or energy ray curable resin layer (I) contains energy ray curable component (a) and polymer (b), the content of polymer (b) is relative to energy ray curable Component (a) is 100 mass parts, Preferably it is 3-160 mass parts, More preferably, it is 6-130 mass parts. When the content of the polymer (b) is in the above range, the energy ray curability can be further improved.

In the energy ray curable resin composition, in addition to the energy ray curable component (a) and the polymer (b), it may contain a photopolymerization initiator (c), a coupling agent (d), and a crosslinking agent according to the purpose. One or more selected from the group consisting of (e), colorant (g), thermosetting component (f), hardening accelerator (g), filler (h) and general-purpose additive (z). For example, when using an energy ray curable resin composition containing an energy ray curable component (a) and a thermosetting component (f), the formed energy ray curable resin layer (I) can be heated to improve The adhesive force of the adherend can also increase the strength of the cured resin layer (I') formed from the energy ray curable resin layer (I).

等的9-氧硫𠮿

化合物；二苯甲酮、2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮、乙酮、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-、1-(O-乙醯肟)等的二苯甲酮化合物；過氧化物化合物；二乙醯基等的二酮化合物；苄基；二苄基；2,4-二乙基氧硫𠮿

；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。又，1-氯蒽醌等的醌化合物；胺等的光増感劑等。    　　光聚合起始劑(c)，可單獨使用亦可、將2種以上合併使用亦可。    　　能量線硬化性樹脂組成物或能量線硬化性樹脂層(I)中，光聚合起始劑(c)之含量，相對於能量線硬化性化合物(a)100質量份，較佳為0.01～20質量份，更佳為0.03～10質量份，特佳為0.05～5質量份。[Photopolymerization initiator (c)] As the photopolymerization initiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Benzoine compounds such as ether, benzoine benzoic acid, methyl benzoine benzoate, benzoine dimethyl ketal, etc.; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane Acetophenone compounds such as -1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, etc.; oxidized bis(2,4,6-trimethylbenzoyl ) phenylphosphine (phosphine), 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other phosphine oxide compounds; benzyl phenyl sulfide, tetramethylthiuram mono Thioether compounds such as sulfide; α-ketol compounds such as 1-hydroxycyclohexyl benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene;

9-oxosulfur

Compounds; benzophenone, 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone, ethyl ketone, 1-[9-ethyl- Benzophenone compounds such as 6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); peroxide compounds; diacetyl Diketone compounds such as; benzyl; dibenzyl; 2,4-diethylsulfuryl 𠮿

; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc. Also, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines; and the like. The photopolymerization initiator (c) may be used alone or in combination of two or more. In the energy ray curable resin composition or the energy ray curable resin layer (I), the content of the photopolymerization initiator (c) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the energy ray curable compound (a). Parts by mass are more preferably 0.03 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.

[Coupling agent (d)] When using a coupling agent (d) that has a functional group that can react with an inorganic compound or an organic compound, it can improve the adhesion of the energy ray-curable resin layer (I), and can also make the The cured resin layer (I') formed by curing the energy ray curable resin layer (I) improves water resistance without impairing its heat resistance. The coupling agent (d) may be used alone or in combination of two or more.

The coupling agent (d) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray curable component (a), polymer (b), etc., and a silane coupling agent is more preferred. Silane coupling agents, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxy Methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(phenylamino ) Propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-acylureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Methyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyl trimethoxysilane Acetyloxysilane, imidazole silane, etc.

In the energy ray curable resin composition or the energy ray curable resin layer (I), the content of the coupling agent (d) is less than 100 parts by mass of the total of the energy ray curable component (a) and the polymer (b). Preferably, it is 0.03-20 mass parts, More preferably, it is 0.05-10 mass parts, Most preferably, it is 0.1-5 mass parts. When the content of the coupling agent (d) is more than the above-mentioned lower limit, the effects of improving the dispersibility of the resin in the filler and improving the adhesiveness of the energy ray-curable resin layer (I) are more remarkable. When it is below the limit value, the generation of outgassing can be suppressed.

[Crosslinking agent (e)] When the energy ray curable component (a), polymer (b), etc. are crosslinked using the crosslinking agent (e), the initial stage of the energy ray curable resin layer (I) can be adjusted. Adherence and cohesion. The crosslinking agent (e) may be used alone or in combination of two or more.

Crosslinking agent (e), for example, organic polyvalent isocyanate compound, organic polyvalent imine compound, metal chelate crosslinking agent (crosslinking agent with metal chelate structure), aziridine (aziridine) Cross-linking agent (cross-linking agent having an aziridine group), etc.

Organic polyvalent isocyanate compounds, such as aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds are also collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate bodies, and adducts of aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the above aromatic polyvalent isocyanate compounds, etc., with polyol compounds wait. The above-mentioned "adduct" refers to the above-mentioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or Reactants of low-molecular-weight active hydrogen-containing compounds such as castor oil, for example, xylene diisocyanate adducts of trimethylolpropane described later. Also, the term "isocyanate-terminated urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a molecular terminal.

Organic polyvalent isocyanate compounds, more specifically, for example, in 2,4-cresyl diisocyanate; 2,6-cresyl diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Trimethylolpropane and other polyalcohols in all or part of the hydroxyl groups, additional Compounds obtained from any one or two or more of cresyl diisocyanate, hexylene diisocyanate and xylene diisocyanate; lysine diisocyanate, etc.

Organic polyvalent imine compounds such as N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxamide), trimethylolpropane-tri-β-aziridine Cyclopropanyl propionate, Tetramethylolmethane-tris-β-Aziridine propionate, N,N'-Toluene-2,4-Bis(1-Aziridinecarboxyamide)triethylenemelamine wait.

When an organic polyvalent isocyanate compound is used as the crosslinking agent (e), it is preferable to use a hydroxyl group-containing polymer for the energy ray curable component (a) and/or the polymer (b). When the crosslinking agent (e) has an isocyanate group and the energy ray-curable component (a) and/or the polymer (b) has a hydroxyl group, the crosslinker (e) and the energy ray-curable component (a) and/or The reaction of the polymer (b) can easily introduce a crosslinked structure into the energy ray curable resin layer (I).

In the energy ray curable resin composition or the energy ray curable resin layer (I), the content of the crosslinking agent (e) is 100 parts by mass of the total of the energy ray curable component (a) and the polymer (b), Preferably it is 0.01-20 mass parts, More preferably, it is 0.1-10 mass parts, Most preferably, it is 0.5-5 mass parts.

[Thermosetting component (f)] Thermosetting component (f), for example, epoxy-based thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, polysilicon epoxy resin, etc., and among them, epoxy-based thermosetting resin is preferable. The thermosetting component (f) may be used alone or in combination of two or more.

(Epoxy-based thermosetting resin) The epoxy-based thermosetting resin contains epoxy resin (f1), which may further contain a thermosetting agent (f2).

Epoxy resins (f1), such as known resins, for example, polyfunctional epoxy resins, bisphenol A diepoxy ethers and their hydrides, o-cresol-novolac epoxy resins, dicyclopentadiene-type epoxy resins, Bifunctional epoxy compounds such as epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. Epoxy resins (f1) may be used alone or in combination of two or more.

Epoxy resin (f1), can use vinyl (ethenyl) (vinyl), 2-propenyl (allyl), (meth)acryl, (meth)acrylamide etc. Saturated hydrocarbon-based epoxy resin. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, when an epoxy resin having an unsaturated hydrocarbon group is used, the reliability of the resulting package can be improved.

The number average molecular weight of the epoxy resin (f1) is preferably from 300 to 30000, more preferably from the viewpoint of the curability of the energy ray curable resin layer (I), and the strength and heat resistance of the cured resin layer (I'). 400-10000, especially 500-3000. The epoxy equivalent of the epoxy resin (f1) is preferably 100-1000 g/eq, more preferably 150-800 g/eq.

The thermosetting agent (f2) functions as a curing agent for the epoxy resin (f1). A thermosetting agent (f2), for example, a compound having two or more functional groups capable of reacting with an epoxy group in one molecule, etc. The above-mentioned functional groups, for example, phenolic hydroxyl group, alcoholic hydroxyl group, amino group, carboxyl group, acid group are anhydrided groups, etc., and phenolic hydroxyl groups, amino groups, or acid groups are preferably anhydrided groups. A phenolic hydroxyl group or an amino group is preferred. The thermosetting agent (f2) can be used alone or in combination of two or more.

Among the thermosetting agents (f2), phenolic curing agents having phenolic hydroxyl groups include, for example, polyfunctional phenolic resins, bisphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. Among the thermal hardeners (f2), amine-based hardeners with amine groups, such as dicyandiamide, etc. The content of the thermosetting agent (f2) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the epoxy resin (f1).

The content of the thermosetting component (f) (for example, the total content of the epoxy resin (f1) and the thermosetting agent (f2)) is preferably 1 to 500 parts by mass based on 100 parts by mass of the polymer (b).

[Hardening accelerator (g)] The hardening accelerator (g) is a component that can adjust the hardening speed of the energy ray-curable resin layer (I). Preferred hardening accelerators (g), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. ; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5 -Imidazoles such as hydroxymethylimidazole; organic phosphines such as tributylphosphine, diphenylphosphinate, triphenylphosphinate; tetraphenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl Tetraphenylboron salts such as phenyl borate and the like. When using a hardening accelerator (g), the content of the hardening accelerator (g) is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the thermosetting component (f).

[Wide-use additive (z)] Wide-use additive (z) can use well-known additives, which can be selected arbitrarily according to the purpose, without special limitations, such as fillers, colorants, plasticizers, antistatic Agents, antioxidants, absorbents, etc. Among the widely used additives (z), each of them may be used alone or in combination of two or more.

The fillers include, for example, inorganic fillers and organic fillers, and when these components are used, the thermal expansion coefficient of the cured resin layer (I') can be adjusted. The energy ray-curable resin layer (I) may or may not contain a filler. When a filler is included, the content will be more effective in suppressing deformation. Compared with the energy ray-curable resin composition The total amount (100% by mass) of active ingredients or the total amount (100% by mass) of the energy ray-curable resin layer (I) is preferably 5 to 87% by mass, more preferably 7 to 78% by mass. Filling materials, for example, those formed from thermally conductive materials. Inorganic fillers, such as powders of silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, red iron oxide, silicon carbide, boron nitride, etc.; spheroidized particles of these inorganic fillers; Surface modified products of inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. The average particle size of the filler is preferably 0.01-20 μm, more preferably 0.1-15 μm, and most preferably 0.3-10 μm. When the average particle size of the filler is within the above range, the adhesiveness of the cured resin layer (I') can be maintained, and the decrease in the transmittance of the energy ray-curable resin layer (I) can be suppressed.

The energy ray-curable resin composition may or may not contain a colorant, and when a colorant is contained, the less the content, the better. Specifically, the energy ray-curable resin composition is effective The total amount (100% by mass) of the components or the total amount (100% by mass) of the energy ray-curable resin layer (I) is preferably less than 5% by mass, more preferably less than 0.1% by mass, most preferably less than 0.01% by mass % by mass, preferably less than 0.001% by mass.

<<Manufacturing method of energy ray curable resin composition>> The energy ray curable resin composition can be prepared by blending the various components constituting the composition. There is no particular limitation on the order of addition when blending the ingredients, and two or more ingredients can be added at the same time. When using a solvent, the solvent can be mixed with any additional ingredients other than the solvent, and the added ingredients can be diluted in advance and stored for use, or any additional ingredients other than the solvent can be diluted and stored in advance, and then the solvent can be mixed with the solvent when used. Some additional ingredients can also be used in combination. When blending, the mixing method of each component is not particularly limited, for example, the method of mixing by rotating a stirring bar or stirring blade; You can choose to use it appropriately. There are no special restrictions on the temperature and time of adding and mixing each component, as long as it does not cause deterioration of each added component, as long as it is properly adjusted, and the temperature is preferably 15-30°C.

The above-mentioned solvents, for example, hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), 1-butanol; ethyl acetate and the like ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone, etc. Among them, it is preferable to use methyl ethyl ketone, toluene, and ethyl acetate from the viewpoint of mixing the components contained in the energy ray-curable resin composition more uniformly. The solvent may be used alone or in combination of two or more.

The energy ray-curable resin layer (I) may be composed of a single layer, or may be composed of a plurality of two or more layers. The energy ray-curable resin layer (I) composed of two or more layers, for example, has an energy ray-curable resin layer (I-i) capable of imparting a cured resin layer (I') having a high storage modulus E', and has Resin layer, etc. of energy ray curable resin layer (I-ii) with high adhesive force. With these configurations, when the energy ray-curable resin layer (I-ii) is placed on the surface on which the object to be sealed is placed, the object to be sealed can be firmly fixed, and after hardening, the energy ray The hardened resin layer (I') obtained by hardening the hardened resin layer (I-i) has the function of effectively suppressing deformation, so it can further improve the performance of the temporary fixing layer and the performance of the deformation-resistant layer. The preferred composition and physical properties of the energy ray-curable resin layers (I-i) and (I-ii) can be made in accordance with the desired functions in the preferred composition and physical properties of the energy ray-curable resin layer (I). Appropriate selection can be used.

The thickness of the energy ray curable resin layer (I) is preferably 1-500 μm, more preferably 5-300 μm, particularly preferably 10-200 μm, most preferably 15-100 μm, most preferably 20-50 μm. When the thickness of the energy ray-curable resin layer (I) is more than the above-mentioned lower limit, a cured sealing body that can more effectively suppress deformation can be obtained. Excellent hardenability is obtained. Here, the "thickness of the energy ray curable resin layer (I)" means the thickness of the entire energy ray curable resin layer (I), for example, the energy ray curable resin layer (I) composed of two or more layers ) means the total thickness of all the layers constituting the energy ray curable resin layer (I).

The storage elastic modulus E' of the hardened resin layer (I') formed by hardening the energy ray-curable resin layer (I) at 23°C is used as an index to obtain a hardened resin layer with a flat surface that can suppress deformation. From the viewpoint of the laminated body of the hardened sealing body, it is preferably at least 1.0×10 ⁷ Pa, more preferably at least 1.0×10 ⁸ Pa, particularly preferably at least 5.0×10 ⁸ Pa, and most preferably at least 1.0×10 ⁹ . Preferably it is 1.0×10 ¹³ Pa or less, more preferably 1.0×10 ¹² Pa or less, particularly preferably 5.0×10 ¹¹ Pa or less, most preferably 1.0×10 ¹¹ Pa or less.

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

<Manufacturing method of laminated body> The laminated body of one aspect of the present invention, for example, can separately form various expectations of the adhesive layer (X), base material (Y) and energy ray curable resin layer (I) The composition content is made by laminating. The formation of each layer can be formed by, for example, coating a resin composition used for forming each layer on a release material, and drying it. However, the method for producing a laminate according to an aspect of the present invention is not limited to the method described above. For example, the formable substrate (Y) can be coated on the adhesive layer (X) formed on the release material. As shown in the method of coating the resin composition (y) of energy ray curable resin composition on it, the resin composition is sequentially coated on a specific layer to form a layer to form a multilayer method. In this case, a plurality of layers can be coated simultaneously using, for example, a multilayer coater (coater).

[Manufacturing method of hardened sealing body] The manufacturing method of the hardened sealing body of one aspect of the present invention is a method of manufacturing a hardened sealing body using the laminated body of one aspect of the present invention, which has the following steps (i) to (iv). Step (i): A step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminate. Step (ii): Irradiating the energy ray-curable resin layer with energy rays (I), the step of forming the cured resin layer (I') formed by hardening the energy ray curable resin layer (I) Step (iii): Hardening the aforementioned sealed object and at least the peripheral portion of the sealed object The surface of the resin layer (I') is covered with a thermosetting sealing material, and the sealing material is thermally cured to form a hardened sealing body containing the aforementioned object to be sealed. Step (iv): After expanding the aforementioned heat-expandable particles The process of separating the hardened resin layer (I') and the support layer (II) at the interface to obtain a hardened sealing body with a hardened resin layer. Also, the hardened sealing body in one aspect of the present invention , refers to the object obtained by covering the object to be sealed with a sealing material and then hardening the sealing material, which is composed of the object to be sealed and the hardened material of the sealing material.

Fig. 4 is a schematic cross-sectional view illustrating the steps of producing a hardened sealing body using the laminated body 1a shown in Fig. 1(a). Hereinafter, the above steps will be described with appropriate reference to FIG. 4 .

<Step (i)> Step (i) is a step of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the laminated body of one aspect of the present invention. Fig. 4(a) illustrates that in the laminated body 1a in this step, the adhesive surface of the adhesive layer (X) of the support layer (II) is attached to the support body 50, so that the energy ray curable resin layer (I) A part of the surface of the surface is the state where the object to be sealed 60 is placed. Also, in FIG. 4(a), in order to illustrate an example using the laminated body 1a shown in FIG. The laminated body and the object to be sealed are laminated or placed in sequence.

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

The support is preferably one that is attached to the entire surface of the adhesive layer (X) of the laminate. Therefore, the support body is preferably in the form of a plate. Also, the surface area of the support attached to the adhesive surface of the adhesive layer (X) is preferably greater than or equal to the adhesive surface area of the adhesive layer (X) as shown in FIG. 4 .

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 characteristics 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, from the viewpoint that the energy ray-curable resin layer (I) can be irradiated with energy rays through a support, the support is preferably made of a transparent material such as glass. In addition, engineering plastics include, for example, nylon, polycarbonate (PC), and polyethylene terephthalate (PET). High-end engineering plastics include, for example, polyphenylene sulfide (PPS), polyether ketone (PES), and polyether-ether ketone (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., preferably 20 μm to 50 mm, more preferably 60 μm to 20 mm.

On the other hand, the object to be sealed where energy lines are placed on a part of the surface of the curable resin layer (I), for example, semiconductor wafers, semiconductor wafers, compound semiconductors, semiconductor packages, electronic parts, sapphire substrates, displays , Substrates for flat panels, etc.

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. The semiconductor chip can be known in the past, and its circuit surface is formed with an integrated circuit composed of circuit elements such as transistors, resistors, and condensers. Next, it is preferable that the semiconductor wafer is placed on the inner surface opposite to the circuit surface so that the surface of the energy ray-curable resin layer (I) is covered. In this case, after mounting, the circuit surface of the semiconductor wafer is exposed. The mounting of the semiconductor chip can be carried out using known devices such as flip-chip bonders and die bonders. The layout and number of configurations of semiconductor chips can be appropriately determined in accordance with the intended packaging form and production quantity.

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 a part of the surface of the curable resin layer (I) where the energy lines are placed, and the plurality of semiconductor chips are preferably placed on the surface in a state of forming rows and rows at a specific distance. , A plurality of semiconductor wafers are preferably mounted on the surface in a matrix-like state of a plurality of rows and a plurality of columns at a predetermined distance apart. The spacing between semiconductor chips can be appropriately determined in accordance with the intended packaging form.

<Step (ii)> Step (ii) is a step of irradiating the energy ray curable resin layer (I) with energy rays to form a cured resin layer (I') formed by curing the energy ray curable resin layer (I) . FIG. 4( b ) illustrates the state in which the energy ray curable resin layer (I) is cured to form the cured resin layer (I') in this step. The type and irradiation conditions of energy rays are not particularly limited as long as they can harden the energy ray-curable resin layer (I) to the extent that it can fully exert its functions. It is properly selected and used according to the expected process. When the energy ray-curable resin layer (I) is hardened, the illuminance of the energy ray is preferably 4-280mW/cm ² , and during the above-mentioned hardening, the illuminance of the energy ray is preferably 5-1000mJ/cm ² , preferably 100-280mW/cm 2 . 500mJ/cm ² is better. The types of energy rays and irradiation devices are as described above. Energy rays can be irradiated in any direction as long as the energy ray-curable resin layer (I) can be irradiated by the energy rays. When the transmittance is higher, it can be injected through the support body (II) and the support body 50 (that is, in FIG. body 50, the adhesive layer (X) and the base material (Y)), the energy ray is irradiated to the energy ray curable resin layer (I).

<Step (iii)> Step (iii) is to cover (hereinafter, also referred to as "coating treatment") the above-mentioned sealed object with a thermosetting sealing material, and the hardened resin layer ( The surface of I') is a step of thermally hardening the sealing material to form a hardened sealing body including the above-mentioned sealing object. In the coating process, first, in order to coat the object to be sealed with a sealing material, at least the peripheral portion of the object to be sealed is between the surface of the hardened resin layer (I'). The sealing material not only covers the entire exposed surface of the object to be sealed, but also fills the gap between multiple semiconductor chips. For example, Fig. 4(c) illustrates the state where the sealing material 70 is used to cover the entire surface of the sealing object 60 and the cured resin layer (I').

The sealing material has the function of protecting the sealing object and its additional elements from the external environment. The sealing material used in the manufacturing method of one aspect of the present invention is a thermosetting sealing material containing a thermosetting resin. In addition, the sealing material can be solid at room temperature, such as granular, granular, and film-like, or it can be liquid in the form of a composition. From the viewpoint of workability, the sealing resin of the film-like sealing material Film is preferred.

The coating method can be appropriately 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, and die coating can be used. Cloth method, transfer injection molding method, compression molding mold method, etc.

Then, after the coating treatment, the sealing material is thermally cured to obtain a hardened sealing body in which the object to be sealed is sealed by the sealing material. Also, the thermosetting treatment in step (iii) is carried out at a temperature at which the heat-expandable particles do not expand. It is better to carry out under the temperature condition of the initial temperature (t).

In the manufacturing method of one aspect of the present invention, as shown in FIG. Heat hardened. Since the hardened resin layer (I') is provided, the shrinkage stress difference between the surfaces of the obtained two hardened sealing bodies can be reduced, and the deformation caused by the hardened sealing body can be effectively suppressed.

<Step (iv)> Step (iv) is that the above-mentioned 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, and the hardened resin layer is obtained. step of hardening the seal. Figure 4(d) illustrates that the heat-expandable particles are subjected to expansion treatment and form a state of separation at the interface P between the hardened resin layer (I') and the support layer (II). As shown in Fig. 4(d), by forming a separation result at the interface P, it is possible to obtain a cured resin with a hardened sealing body 80 and a hardened resin layer (I') formed by sealing the object 60 to be sealed. layer of hardened sealant 100 . In addition, the existence of the hardened resin layer (I') not only has the function of effectively suppressing the deformation caused by the hardened sealing body, but also protects the object to be sealed, thereby improving the reliability of the object to be sealed.

"Performing expansion treatment" in step (iv) refers to heating the heat-expandable particles to a temperature above the expansion initiation temperature (t), subjecting the heat-expandable particles to expansion treatment, and through this treatment, the hardened resin layer (I') The surface of the supporting layer (II) on the side is uneven. As a result, the interface P can be easily separated as a whole with a little force. "Temperature above the expansion start temperature (t)" when expanding the heat-expandable particles refers to "expansion start temperature (t) + 10°C" or more and "expansion start temperature (t)+60°C" or less Preferably, it is more than "expansion initiation temperature (t) + 15°C" and more preferably "expansion initiation temperature (t) + 40°C". Also, the heating method is not particularly limited. For example, heating methods such as a heating plate, an oven, a sintering furnace, an infrared lamp, and a hot air blower can be used to make the interface between the support layer (II) and the hardened resin layer (I') From the viewpoint of easy separation of P, it is preferable that the heat source during heating be installed on the side of the support body 50 .

The hardened sealing body with the hardened resin layer obtained in this way can then be subjected to necessary processing. An example thereof is described below. In addition, in the following description, the object to be sealed 60 will be described using a semiconductor wafer 60 .

<First Grinding Step> In Fig. 5(a), the hardened sealing body 100 with a hardened resin layer obtained according to the above-mentioned manufacturing method is shown. In Fig. 5(b), the pair of grinding means 110 and the hardened sealing body 80 The cured resin layer (I') is ground on the opposite side 100a to expose the circuit surface 60a of the semiconductor wafer 60 in the first grinding step. The grinding means 110 is not particularly limited, and for example, a known grinding device such as a grinder can be used. When implementing the first grinding step, it is better to fix the surface of the hardened resin layer (I') side of the hardened sealing body on another support body from the viewpoint of workability. Also, from the viewpoint of workability, before the first grinding step, it can be cut into a specific size including one or multiple wafers.

<Steps of wire redistribution layer (RDL) and forming external terminal electrodes> In FIG. 5(c), to illustrate the formation of a circuit on the circuit surface 60a of the semiconductor chip 60 exposed on the surface of the hardened sealing body 80 through the first grinding step The wire redistribution layer (RDL) 200 connected, and the step of forming the wire redistribution layer (RDL) of the external terminal electrode 300 and forming the external terminal electrode. The material of the wire redistribution layer (RDL) 200 is not particularly limited as long as it is a conductive material. For example, it can be metals such as gold, silver, copper, aluminum, or alloys containing these metals. The wire redistribution layer (RDL) 200 can be formed using a known method such as a subtractive process or a semi-additive process, and if necessary, one or more insulating layers can be provided. The external terminal electrode 300 forms a circuit connection with the external electrode pad of the wire redistribution layer (RDL) 200 . The external electronic electrodes 300 can be formed, for example, by soldering and joining solder balls.

<Cutting Step> In FIG. 5( d ), the step of cutting the hardened sealing body 100 with a hardened resin layer connected to the external terminal electrode 300 is described.  Dicing can be carried out in the form of one unit of semiconductor wafer, or can be cut with a specific size including multiple semiconductor wafers. The method of cutting the cured sealing body 100 with the cured resin layer is not particularly limited, and cutting means such as a dicing saw can be used for cutting.

<Second Grinding Step> In FIG. 5(e), the grinding means 110 is used to illustrate the grinding of the hardened resin layer (I') disposed on the opposite side to the lead wire redistribution layer (RDL) 200 of the hardened sealing body 80. Second grinding step. At this time, it is preferable to fix the surface of the hardened sealing body 80 on the wire redistribution layer (RDL) 200 side using a back grinding table (BACK GRINDING TABLE). The grinding means 110 is, for example, the same means as the first grinding step. In the second grinding step, a part of the hardened resin layer (I') can be ground, or the entire hardened resin layer (I') can be ground. The method of grinding the hardened resin layer (I') can make the obtained semiconductor package more miniaturized. Therefore, from this point of view, it is preferable to grind all the cured resin layer (I'). On the other hand, if the second grinding step is not carried out, or if only a part of the hardened resin layer (I') is carried out, the hardened resin layer (I') also has the function of protecting the inner surface of the semiconductor chip 60. [Example]

This embodiment will be specifically described using the following examples, but the present invention is not limited by the following examples. In addition, in the following description, curable resin layer (I) refers to both "energy ray curable resin layer (I)" and "thermosetting resin layer". In addition, the physical property values in each example are the values measured according to the following methods.

<Mass average molecular weight (Mw)> Using a gel permeation chromatography analyzer (manufactured by Tosoh Co., Ltd., product name "HLC-8020"), the measurement was carried out under the following conditions, and the measurement was based on standard polystyrene conversion value. (Measurement conditions) ・Tube column: connect "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", "TSK gel G1000HXL" in sequence (all are manufactured by Tosoh Co., Ltd.)・Column temperature: 40℃ ・Evolving solvent: tetrahydrofuran ・Flow rate: 1.0mL/min

<Measurement of the thickness of each layer> The measurement was carried out using a constant pressure thickness tester manufactured by TECLOCK Co., Ltd. (model: "PG-02J", standard specifications: JIS K6783, Z 1702, Z 1709).

<Measurement method of the expansion start temperature (t) and maximum expansion temperature of heat-expandable particles> The expansion start temperature (t) of the heat-expandable particles used in each example was measured according to 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 as the measurement object, and cover the sample with an aluminum cover (diameter 5.6mm, thickness 0.1mm). Using a dynamic viscoelasticity measuring 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 the 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). In addition, the maximum expansion temperature is the temperature at which the displacement measured by the above method reaches the maximum.

<Evaluation of deformation> The curable resin layer (I) of the sheet for forming the curable resin layer (I) prepared in each example was attached to a silicon wafer (size: 12 inches, thickness: 100 μm). Then, a resin composition obtained by mixing an epoxy resin (manufactured by STRUERS, product name "EPO-FIX resin") and a curing agent (manufactured by STRUERS, product name "EPO-FIX hardener") was prepared as a thermosetting resin composition. A resin composition was applied to a thickness of 30 μm on the surface of the silicon wafer opposite to the curable resin layer (I). In this way, the measurement samples before curing are obtained in the order of curable resin layer (I)/silicon wafer/thermosetting resin composition layer. Next, when the curable resin layer (I) is an energy ray curable resin layer (I), use an ultraviolet irradiation device RAD-2000 (manufactured by Linde Co., Ltd.) to irradiate ultraviolet rays with a light intensity of 215mW/cm ² and a light intensity of 187mJ/ The condition of cm ² is irradiated three times to harden the energy ray curable resin layer (I) to form a cured resin layer (I'). Moreover, when curable resin layer (I) is a thermosetting resin layer (I), it can heat at 180 degreeC for 60 minutes, and can form curable resin layer (I'). Thereafter, the thermosetting resin composition was heated and cured to form a thermosetting resin layer, and a cured measurement sample having the order of cured resin layer (I′)/silicon wafer/thermosetting resin layer was prepared. Place the hardened test sample on a horizontal bed, observe visually, and evaluate whether there is deformation according to the following criteria. In addition, the "silicon wafer/thermosetting resin layer" part of the sample measured after curing is equivalent to the composition of a hardened seal formed by sealing a semiconductor chip with a thermosetting resin, so this evaluation result can be used as a Evaluation of the anti-deformation layer performance of the hardened resin layer (I'). 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. Also, in the case where the curable resin layer (I) was not attached, the amount of deformation of the silicon wafer/thermosetting resin layer was 15 mm in the same procedure as above.

<Evaluation of separability> After attaching a silicon wafer to the surface of the curable resin layer (I) of the laminates obtained in each example, the curable resin layer (I) was cured with energy rays or heat energy to form a cured resin layer (I'). Then, the expandable base material layer (Y1) was expanded through heat expansion treatment to separate the cured resin layer (I') from the support layer (II), and then the separation property was evaluated based on the following criteria. In addition, the curing conditions of the curable resin layer (I) obtained in each example, and the thermal expansion treatment conditions of the support layer (II) are the same conditions as those described in Examples 1 to 5 and Reference Example 1 described later. . A: Separation can be formed, and the appearance of the hardened resin layer (I’) is good without paste residue. B: Separation can be formed. Although the appearance of the hardened resin layer (I’) is good, some paste remains. C: Separation cannot be formed, or paste remains on the hardened resin layer (I'), or the appearance of the hardened resin layer (I') is poor.

<Storage elastic modulus E' of the expansive substrate layer (Y1)> Cut out the prepared expansive substrate layer (Y1) with a thickness of 200 μm for the measurement of the storage elastic modulus E' to a length of 5 mm × width 30 mm × thickness of 200 μm After the size, remove the peeling material as the test sample. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800"), under the conditions of test start temperature 0°C, test end temperature 300°C, heating rate 3°C/min, vibration frequency 1 Hz, and amplitude 20 μm, the Measure the storage elastic modulus E' of the test sample at a specific temperature.

<Storage shear elastic modulus G' of the first adhesive layer (X1) and the second adhesive layer (X2)> Cut the first adhesive layer (X1) and the second adhesive layer (X2) into diameters For a circular shape of 8mm, remove the peeling material, and stack them to form a thickness of 3mm, which is used as a test sample. Using a viscoelasticity measurement device (manufactured by Anton Paar, device name "MCR300"), the spiral shear was used under the conditions of the test start temperature 0°C, test end temperature 300°C, temperature rise rate 3°C/min, and vibration frequency 1Hz. Method to measure the storage shear elastic modulus G' of the test sample at a specific temperature.

<Storage modulus E' of cured resin layer (I')> Using the cured resin layer (I) obtained in each example after curing as a test piece, a dynamic viscoelasticity measuring device (manufactured by TA Instruments, product name "DMAQ800") was used. ”), under the conditions of test start temperature 0°C, test end temperature 300°C, heating rate 3°C/min, vibration frequency 11Hz, amplitude 20μm, at 23°C, measure the formed hardened resin layer (I') The storage elastic rate E'. In addition, in the test piece, when the curable resin layer (I) is the energy ray curable resin layer (I), the ultraviolet irradiation device RAD-2000 (manufactured by Linde Co., Ltd. ⁾ , The light quantity 187mJ/cm ² is irradiated three times to make it harden, and when the curable resin layer (I) is a thermosetting resin layer (I), it is used to heat harden at 180°C for 60 minutes.

Synthesis Example 1 (Synthesis of "Urethane Acrylic Resin" used in the expandable substrate layer (Y1)) In a reaction vessel under a nitrogen atmosphere, polycarbonate diol (carbonic acid ester diol) 100 parts by mass, add isophorone diisocyanate in such a way that the equivalent ratio of the hydroxyl group of polycarbonate diol to the isocyanate group of isophorone diisocyanate is 1/1, and then add 160 parts by mass of toluene , stirred under a nitrogen atmosphere, and then reacted at 80°C for more than 6 hours until the concentration of isocyanate groups reached the theoretical amount. Next, a solution obtained by diluting 1.44 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) with 30 parts by mass of toluene was added, and the reaction was carried out at 80° C. for 6 hours until the isocyanate groups at both ends disappeared, and A urethane prepolymer with a mass average molecular weight of 29,000 was obtained. Subsequently, 100 parts by mass of the urethane prepolymer obtained above, 117 parts by mass of methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (2- 5.1 parts by mass of HEMA), 1.1 parts by mass of 1-thioglycerol, and 50 parts by mass of toluene were heated up to 105° C. while stirring. Subsequently, 210 parts by mass of toluene diluted with 2.2 parts by mass of a free radical initiator (manufactured by Japan Finechem Co., Ltd., product name "ABN-E") was added to the reactor at 105°C for 4 hours. The resulting solution was dropped into it. After the dropping, the reaction was carried out at 105°C for 6 hours to obtain a solution of urethane acrylate resin with a mass average molecular weight of 105,000.

[Manufacturing of the sheet for forming the support layer (II)] Production Example 1 (Support layer (II-A)) The sheet forming the support layer (II-A) was produced in the following order (1-1) to (1-4) . The details of the materials used to form each layer are as follows.

<Adhesive resin> ・Acrylic copolymer (i): has a raw material list consisting of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio) An acrylic copolymer with a structural unit Mw of 600,000.・Acrylic copolymer (ii): has the composition of n-butyl acrylate (BA) / methyl methacrylate (MMA) / 2-hydroxyethyl acrylate (HEA) / acrylic acid = 86.0/8.0/5.0/1.0 (Mass ratio) An acrylic copolymer having a Mw of 600,000 structural units derived from raw material monomers to be formed. <Additives> ・Isocyanate crosslinking agent (i): manufactured by Tosoh Co., Ltd., product name "CORONATE L", solid content concentration: 75% by mass. <Heat-expandable particles> ・Heat-expandable particles A: manufactured by KUREHA Co., Ltd., product name "S2640", expansion start temperature (t) = 208°C, average particle size (D ₅₀ ) = 24 μm, 90% particle size (D ₉₀ )=49 μm. <Release material> ・Heavy release film: Linde Co., Ltd., product name "SP-PET382150", one side of a polyethylene terephthalate (PET) film, with a silicone-based release agent The thickness of the formed release agent layer: 38 μm.・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.

(1-1) Formation of the first adhesive layer (X1) To 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (i) as an adhesive resin, 5.0 parts by mass of the above-mentioned isocyanate-based crosslinking agent (i) was added , after dilution with toluene and uniform stirring, an adhesive composition with a solid content concentration (active component concentration) of 25% by mass was prepared. Subsequently, apply the adhesive composition on the surface of the release agent layer of the above-mentioned heavy release film (hereinafter, "release treatment surface") to form a coating film, and dry the coating film at 100°C for 60 seconds to form The first adhesive layer (X1) of the non-thermally expandable adhesive layer with a thickness of 5 μm. Also, at 23°C, the storage shear modulus G'(23) of the first adhesive layer (X1) was 2.5×10 ⁵ Pa. In addition, the adhesive strength at 23° C. of the first adhesive layer (X1) measured based on the above-mentioned method was 0.3 N/25 mm.

(1-2) Formation of the second adhesive layer (X2) To 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (ii) as an adhesive resin, add 0.8 parts by mass of the above-mentioned isocyanate-based crosslinking agent (i) , after dilution with toluene and uniform stirring, an adhesive composition with a solid content concentration (active component concentration) of 25% by mass was prepared. Subsequently, apply the adhesive composition on the release-treated surface of the above-mentioned light release film to form a coating film, and dry the coating film at 100° C. for 60 seconds to form a second adhesive layer (X2) with a thickness of 10 μm. ). Also, at 23°C, the storage shear modulus G'(23) of the second adhesive layer (X2) was 9.0×10 ⁴ Pa. Also, the adhesive force of the second adhesive layer (X2) at 23° C. measured based on the above-mentioned method was 1.0 N/25 mm.

(1-3) Preparation of base material (Y) In 100 parts by mass of the solid content of the urethane acrylate resin prepared in Synthesis Example 1, and 6.3 parts by mass of the above-mentioned isocyanate crosslinking agent (i), add 1.4 parts by mass of dioctyltin bis(2-ethylhexanoate) as a catalyst, and the above-mentioned thermally expandable particles A were diluted with toluene and stirred uniformly to obtain a solid content concentration (active component concentration) of 30 mass % resin composition. Also, the content of the heat-expandable particles A was 20% by mass relative to the total amount (100% by mass) of the active ingredients in the obtained resin composition. Subsequently, this resin composition was coated on a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., product name "COSMO-SHUNE A4100") with a thickness of 50 μm as a non-expandable substrate, stretched Strength value: 0mN/5mmφ) A coating film was formed on the surface, and the coating film was dried at 100°C for 120 seconds to form an expansive substrate layer (Y1) with a thickness of 50 μm. Among them, the PET film of the above-mentioned non-expandable substrate is equivalent to the non-expandable substrate layer (Y2). According to the above method, a substrate (Y) formed by an intumescent substrate layer (Y1) with a thickness of 50 μm and a non-expandable substrate layer (Y2) with a thickness of 50 μm was prepared.

In addition, the sample for measuring the storage elastic modulus E' and the tensile strength value of the expandable base material layer (Y1) is to apply the resin composition to form a coating film on the release-treated surface of the above-mentioned light release film, and make the The coating film was dried at an atmospheric temperature of 100° C. for 120 seconds to form an expansive substrate layer (Y1) with a thickness of 200 μm in the same manner. Subsequently, the storage modulus and tensile strength of the expandable substrate layer (Y1) at various temperatures were measured based on the above-mentioned measurement method. The measurement results are shown below.・Storage elastic modulus E'(23)=2.0×10 ⁸ Pa at 23°C ・Storage elastic modulus E'(100)=3.0×10 ⁶ Pa at 100°C ・Storage elastic modulus E'(208 at 208°C )=5.0×10 ⁵ Pa ・Tensile strength value=0mN/5mmφ

(1-4) Lamination of each layer In the non-expandable substrate layer (Y2) of the substrate (Y) prepared according to the above (1-3), and the second layer formed by the above (1-2) At the same time as bonding the adhesive layer (X2), the expandable base material layer (Y1) is bonded to the first adhesive layer (X1) formed in (1-1) above. Then, according to the sequential layer of light peel film/second adhesive layer (X2)/non-intumescent substrate layer (Y2)/expandable substrate layer (Y1)/first adhesive layer (X1)/heavy peel film Together, a sheet for forming a support layer (II-A) was obtained.

Production Example 2 (Support layer (II-B)) In Production Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles B, and the drying conditions after coating the resin composition to form a coating film were changed to atmospheric temperature Except for the treatment at 100° C. for 1 minute, the same method as in Production Example 1 was followed to prepare a support layer (II-B) forming sheet.・Thermally expandable particles B: Made by Japan Ferrite Co., Ltd., product name "031-40DU", expansion initiation temperature (t) = 80°C.

Production Example 3 (Support layer (II-C)) In Production Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles C, and the drying conditions after coating the resin composition to form a coating film were changed to atmospheric temperature Except for the treatment at 100° C. for 1 minute, the other methods were the same as in Production Example 1 to prepare a sheet for forming a support layer (II-C).・Thermally expandable particles C: Made by Japan Ferrite Co., Ltd., product name "053-40DU", expansion initiation temperature (t) = 100°C.

Also, in Production Examples 2 and 3, when forming the support layer (II) sheet, the drying temperature after coating the resin composition to form a coating film was higher than the expansion initiation temperature (t) of the thermally expandable particles by High, but because the above-mentioned drying temperature is atmospheric temperature, no foaming phenomenon was found on the formed support layer (II).

Production Example 4 (Support layer (II-D)) In Production Example 1, except that the thermally expandable particles A were changed to the following thermally expandable particles D, and the drying conditions after coating the resin composition to form a coating film were changed to atmospheric temperature Except for the treatment at 100° C. for 1 minute, the other methods were the same as in Production Example 1 to prepare a sheet for forming a support layer (II-D).・Thermally expandable particles D: Made by Japan Ferrite Co., Ltd., product name "920-40DU", expansion initiation temperature (t) = 120°C.

[Preparation of sheet for forming curable resin layer (I)] Production Example 5 (Energy Ray Curable Resin Layer (I-A)) Blend the types and amounts shown below (either of which is "active ingredient ratio") Each component is diluted with methyl ethyl ketone and stirred uniformly to obtain a solution of a curable composition with a solid content concentration (active component concentration) of 61% by mass. [(a2) component] ・Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA"): 17.6 parts by mass [(b) component] ・Acrylic polymer: butyl acrylate (BA) (55 parts by mass), methyl acrylate (MA) (10 parts by mass), epoxy methacrylate (GMA) (20 parts by mass) and 2-hydroxyethyl acrylate (HEA) (15 parts by mass) copolymerized Formed acrylic resin (glass transition temperature: -28°C, Mw: 800,000): 17 parts by mass [(c) component] ・Phenyl 1-hydroxycyclohexanone (manufactured by BASF Corporation, product name "IRGACURE-184" ): 0.5 parts by mass [(d) component] ・Epoxy-containing oligomer type silane coupling agent (manufactured by Mitsubishi Chemical Corporation, product name "MSEP2"): 0.6 parts by mass [(e) component] ・TDI Cross-linking agent (Toyo Chemical Co., Ltd., product name "BHS-8515"): 0.5 parts by mass [(f) component] ・Liquid bisphenol A epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name "BPA328"): 16 parts by mass ・Dicyclopentadiene-type epoxy resin (manufactured by Nippon Shokubai Co., Ltd., product name "XD-1000L"): 18 parts by mass ・Dicyclopentadiene-type epoxy resin ( DIC Co., Ltd., product name "HP-7200HH"): 27 parts by mass ・Dicyandiamide (manufactured by ADEKA Co., Ltd., product name "ADEKA Partner 3636AS"): 1.5 parts by mass [(g) component] ・・Imidazole (manufactured by Shikoku Chemical Industry Co., Ltd., product name "2PH-Z"): 1.5 parts by mass

Apply the solution of curable composition prepared by the above method on the peeling surface of the above light release film to form a coating film, and dry the coating film at 120°C for 2 minutes to form an energy beam with a thickness of 25 μm For the curable resin layer (I-A), a sheet for forming the energy ray curable resin layer (I-A) formed by the energy ray curable resin layer (I-A) and the light release film was produced.

Manufacturing Example 6 (Energy Ray Curable Resin Layer (I-B)) Blend the ingredients of the types and amounts shown below (either of which are "active ingredient ratios"), then dilute with methyl ethyl ketone, and evenly Stirring was performed to prepare a solution of a curable composition having a solid content concentration (active component concentration) of 61% by mass. [Ingredient (a2)] ・ε-caprolactone-denatured tris-(2-acryloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "A-9300-1CL") , 3-functional ultraviolet curable compound): 10 parts by mass [(b) component] ・Acrylic resin: methyl acrylate (MA) (85 parts by mass)/2-hydroxyethyl acrylate (HEA) (15 parts by mass) Acrylic resin formed by copolymerization: 28 parts by mass [(c) component] ・2-(dimethylamino)-1-(4-morpholino phenyl)-2-benzyl-1- Butanone (manufactured by BASF Corporation, product name "Irgacure (registered trademark) 369"): 0.6 parts by mass [(d) component] ・3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. Co., Ltd., product name "KBM-503"): 0.4 parts by mass [(h) component] ・Silica filler (fused silica filler, average particle size 8 μm): 57 parts by mass [(z) component] ・Consisting of Phthalocyanine cyan pigment (Pigment Blue 15:3) 32 mass parts, and isoindolinone (indolinone) system yellow pigment (Pigment Yellow 139) 18 mass parts, and anthraquinone system red pigment (Pigment Red 177) 50 mass parts The pigment obtained by mixing the total amount of the above three kinds of pigments/the amount of styrene acrylic resin = 1/3 (mass ratio): 4 parts by mass

Apply the solution of curable composition prepared by the above method on the peeling surface of the above light release film to form a coating film, and dry the coating film at 120°C for 2 minutes to form a thickness of 25 μm The energy ray curable resin layer (I-B), and then the sheet for forming the energy ray curable resin layer (I-B) formed by the energy ray curable resin layer (I-B) and the light release film.

Production Example 7 (Thermosetting resin layer (I-C)) After blending the ingredients of the types and amounts shown below (either of which are "active ingredient ratios"), dilute with methyl ethyl ketone and stir evenly , and a solution of a curable composition with a solid content concentration (active component concentration) of 61% by mass was prepared.・Acrylic polymer: butyl acrylate (BA) (1 part by mass), methyl acrylate (MA) (74 parts by mass), epoxy methacrylate (GMA) (15 parts by mass) and 2-hydroxy acrylate Ethyl (HEA) (10 parts by mass) copolymerized acrylic resin (glass transition temperature: 8°C, Mw: 440,000): 18 parts by mass ・Liquid bisphenol A epoxy resin (Nippon Shokubai Co., Ltd. Made by the company, product name "BPA328"): 3 parts by mass ・Solid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "EPIKOTE 1055"): 20 parts by mass ・Dicyclopentadiene type epoxy Resin (manufactured by Nippon Kayaku Co., Ltd., product name "XD-1000L"): 1.5 parts by mass ・Dicyandiamide (manufactured by ADEKA Corporation, product name "ADEKA Partner 3636AS"): 0.5 parts by mass ・Imidazole (Shikoku Kasei Kogyo Co., Ltd., product name "2PH-Z"): 0.5 parts by mass ・Epoxy-containing oligomer type silane coupling agent (manufactured by Mitsubishi Chemical Co., Ltd., product name "MSEP2"): 0.5 parts by mass・Spherical silica filler (manufactured by ADMATECHS Co., Ltd., product name "SC2050MA"): 6 parts by mass ・Spherical silica filler (Longsen Co., Ltd., product name "SV-10"): 50 parts by mass

Apply the solution of the curable composition prepared by the above method on the peeling surface of the above light release film to form a coating film, and dry the coating film at 120°C for 2 minutes to form a 25 μm thick film. Thermosetting resin layer (I-C), and then make a sheet for forming thermosetting resin layer (I-C) formed by thermosetting resin layer (I-C) and light release film.

[Manufacture of laminated body] Examples 1-5, Reference Example 1 Remove the support layer (II) formation sheet shown in Table 1 and peel off the film so that the first adhesive layer (X1) exposed is the same as that shown in Table 1. The surface of the curable resin layer (I) of the curable resin layer (I) forming sheet shown was bonded together to obtain a laminate. In addition, in Example 5, Nitto Denko Co., Ltd. product name "REVALPHA 3195" (expansion initiation temperature (t) = 170° C.) was used as the support layer (II-E) forming sheet.  The evaluation results of separation and deformation of the laminates obtained in each example are shown in Table 1.

[Production of hardened sealing body] Then, using the laminated body obtained in each example, the hardened sealing body was produced in the following order.

(1) Mounting of the semiconductor wafer Remove the light release film on the support layer (II) side of the laminate, and attach the exposed adhesive surface of the second adhesive layer (X2) of the support layer (II) to the support body (glass). Subsequently, the light release film on the side of the curable resin layer (I) is also removed, and on the surface of the exposed curable resin layer (I), the inner surface on the opposite side to the circuit surface of each semiconductor chip is in contact with the curable resin layer. In the form of the surface of (I), nine semiconductor wafers (each wafer size is 6.4 mm x 6.4 mm and wafer thickness is 200 μm (♯2000)) are placed at necessary intervals.

(2) Formation of the cured resin layer (I') In Examples 1 to 5, after the above (1) and before the following (3), ultraviolet (UV) irradiation is used as the energy ray of the curable resin layer (I) The hardening resin layer (I) is formed to form the hardening resin layer (I') on which the semiconductor wafer is placed. In addition, ultraviolet rays were irradiated three times from the support (glass) side under conditions of illuminance 215 mW/cm ² and light intensity 187 mJ/cm ² using an ultraviolet irradiation device RAD-2000 (manufactured by Linde Corporation). Also, in Reference Example 1, the step (2) is not implemented, and in the step (3) described later, in the process of curing the sealing material, the thermosetting resin layer as the curable resin layer (I) is simultaneously cured. .

(3) Formation of hardened sealing body The thermosetting sealing resin film of the sealing material is used to cover the above-mentioned 9 semiconductor wafers, and the hardened resin layer (I') of at least the peripheral portion of the semiconductor wafer (in reference example 1, On the surface of the thermosetting resin layer), the sealing resin film was thermally cured using a vacuum heat press laminator (manufactured by ROHM and HAAS, product name "7024HP5") to obtain a cured sealing body. In addition, the sealing conditions are as follows.・Preheating temperature: 100°C for bed and diaphragm (diaphragm) ・Vacuum stretching: 60 seconds ・Dynamic pressurization mode: 30 seconds ・Static pressurization mode: 10 seconds ・Sealing temperature: 180°C× 60 minutes

(4) Separation of the interface P After the above (3), the heat-expandable particles contained in the support layer (II) of each laminate are subjected to heat-expansion treatment at the temperature of the expansion initiation temperature (t) + 30°C for 3 minutes , to separate the interface P between the first adhesive layer (X1) of the support layer (II) and the cured resin layer (I′). In this manner, a hardened sealing body with a hardened resin layer is produced.

As can be seen from the results in Table 1, in Examples 1 to 5 using the laminate of an aspect of the present invention, the formed cured sealant was not deformed, and the support layer (II) had excellent separability. On the other hand, in Reference Example 1 where a thermosetting resin layer was used as the curable resin layer, the cured resin layer (I') could not be separated from the support layer (II).

1a, 1b, 2a, 2b, 3: laminate (I): energy ray curable resin layer (I'): curable resin layer (II): support layer (X): adhesive layer (X1): first adhesive Agent layer (X2): Second adhesive layer (Y): Base material (Y1): Expandable base material layer (Y2): Non-expandable base material layer 50: Support body 60: Object to be sealed (semiconductor wafer) 70 : Sealing material 80: Hardened sealing body 100: Hardened sealing body with hardened resin layer 100a: Surface of hardened sealing body 110: Grinding means 200: Conductor wire redistribution layer (RDL) 300: External terminal electrode

[FIG. 1] A schematic cross-sectional view of the laminate illustrating the constitution of the laminate according to the first aspect of the present invention. [FIG. 2] A schematic cross-sectional view of the laminate illustrating the constitution of the laminate according to the second aspect of the present invention. [FIG. 3] A schematic cross-sectional view of the laminate illustrating the constitution of the laminate according to the third aspect of the present invention. [FIG. 4] A cross-sectional schematic diagram illustrating the steps of manufacturing a hardened sealing body with a hardened resin layer using the laminated body 1a shown in FIG. 1(a). [Fig. 5] It is a schematic cross-sectional view illustrating the processing method of the hardened sealing body.

1a, 1b: laminate

P: interface

(X): adhesive layer

(Y): Substrate

(Y1): Expandable substrate layer

(Y2): Non-intumescent substrate layer

(I): Energy ray curable resin layer

(II): support layer

Claims (11)

A laminate characterized by having an energy ray-curable resin layer (I), and a support layer (II) supporting the energy ray-curable resin layer (I); the energy ray-curable resin layer (I) having Adhesive surface, the support layer (II) has a base material (Y) and an adhesive layer (X), at least one of the base material (Y) and the adhesive layer (X) contains thermally expandable particles, and is formed by Between the cured resin layer (I') formed by hardening the energy ray curable resin layer (I) and the support layer (II), the heat-expandable particles are expanded, and between the cured resin layer (I') and the support layer The interface of layer (II) forms a separation. The laminate according to claim 1, wherein the storage elastic modulus E' at 23°C of the cured resin layer (I') formed by curing the energy ray curable resin layer (I) is 1.0×10 ⁷ to 1.0×10 ¹³ Pa. The laminate according to claim 1 or 2, wherein the thickness of the energy ray curable resin layer (I) is 1 to 500 μm. The laminate according to claim 1 or 2, wherein the visible light transmittance of the energy ray curable resin layer (I) is 5% or more. The laminate according to claim 1 or 2, wherein the substrate (Y) has The expandable base material layer (YI) of the said thermally expandable particle. The laminate according to claim 5, wherein the adhesive layer (X) is a non-expandable adhesive layer. The laminate according to claim 5, wherein the adhesive layer (X) and the energy ray curable resin layer (I) are directly laminated. 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 The layer (Y2), the expandable substrate layer (Y1), and the adhesive layer (X), the adhesive layer (X) and the energy ray curable resin layer (I) are directly laminated. The laminated body according to claim 1 or 2, which is used to form a hardened sealing body containing a sealed object, wherein the sealed object is placed on a part of the surface of the energy ray curable resin layer (I), so that The energy ray irradiates the energy ray curable resin layer (I) to form a cured resin layer (I') formed by hardening the energy ray curable resin layer (I), on the aforementioned sealing object, and at least the periphery of the sealing object Part of the surface of the cured resin layer (I') is covered with a thermosetting sealing material, After the sealing material is thermally cured, the heat-expandable particles are expanded, so that the hardened resin layer (I') and the support layer (II) are formed at the interface between the hardened resin layer (I') and the support layer (II) separate. The laminated body according to claim 9, which is used to prevent warpage of the aforementioned hardened sealing body. A method of manufacturing a hardened sealing body, which is a method of manufacturing a hardened sealing body using the laminate in any one of Claims 1 to 10, characterized in that it has the following steps (i) to (iv): Step (i) : Step (ii) of placing an object to be sealed on a part of the surface of the energy ray-curable resin layer (I) of the aforementioned laminate: irradiating the energy ray-curable resin layer (I) with energy rays, The step of forming the cured resin layer (I') formed by hardening the energy ray curable resin layer (I) Step (iii): On the aforementioned sealing object, the hardened resin layer (I') on at least the peripheral portion of the sealing object The surface of ') is covered with a thermosetting sealing material, and the sealing material is thermally cured to form a hardened sealing body containing the aforementioned object to be sealed Step (iv): After the treatment of expanding the aforementioned thermally expandable particles, harden The resin layer (I') and the supporting layer (II) are separated at the interface between the hardened resin layer (I') and the aforementioned supporting layer (II) to obtain a hardened sealing body with a hardened resin layer.

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