TWI797272B - Processed product manufacturing method and adhesive laminate - Google Patents

Abstract

The present invention relates to a method of manufacturing a processed product, which is a method of manufacturing a processed product subjected to at least one of cutting and grinding using an adhesive laminate, the adhesive laminate comprising: a substrate (Y1) and an adhesive agent layer (X1), and a heat-expandable adhesive sheet (I) containing heat-expandable particles having a thermal expansion start temperature (t) in any layer, and an adhesive sheet (I) having a base material (Y2) and an adhesive layer (X2) ( II), and it is formed by direct lamination of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), The aforementioned manufacturing method has the following steps (1) to (3) in sequence, ・Step (1): The step of attaching the surface of the adhesive layer (X1) of the aforementioned adhesive laminate to the support, and attaching an additional object to the surface of the adhesive layer (X2) of the aforementioned adhesive laminate ; ・Step (2): A step of applying one or more processes to the aforementioned object to be processed; ・Step (3): By heating above the thermal expansion start temperature (t) of the thermally expandable particles, while maintaining the state where the object to be processed is attached to the surface of the adhesive layer (X2) of the adhesive laminate, A step of separating the aforementioned adhesive laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II); Furthermore, the following step (4) is provided, ・Step (4): A step of performing at least one of cutting and grinding on the surface of the aforementioned object to be processed which is opposite to the surface to which the adhesive layer (X2) is attached; The aforementioned step (4) is implemented in at least one of the following (X) and (Y), (X): As one or more of the above-mentioned processings, it is implemented in the aforementioned step (2); (Y): implemented after the aforementioned step (3).

Description

Processed product manufacturing method and adhesive laminate

The present invention relates to a method of manufacturing a processed product subjected to at least one of cutting and grinding, and an adhesive laminate using the manufacturing method.

Adhesive sheets are used not only for semi-permanent fixing of components, but also for temporary fixing when temporarily fixing target components when processing or inspecting building materials, interior materials, and electronic parts, etc. . Adhesive sheets for such temporary fixation are required to have both adhesiveness during use and peelability after use.

For example, Patent Document 1 discloses a heat-peelable adhesive sheet for temporarily fixing electronic components when cutting electronic components provided with a heat-expandable adhesive layer containing heat-expandable microspheres on at least one surface of a substrate. In the heat-peelable adhesive sheet, the thickness of the heat-expandable adhesive layer is adjusted by adjusting the maximum particle size of the heat-expandable microspheres, and the average thickness of the centerline of the surface of the heat-expandable adhesive layer before heating is adjusted to be 0.4 μm or less. It is described in Patent Document 1 that when the heat-peelable adhesive sheet is cut, the contact area with the adherend can be ensured, and the adhesiveness can prevent the adhesion failure such as chip flying out. On the other hand, after use, , When the heat-expandable microspheres are expanded by heating and the contact area with the adherend is reduced, the contents can be easily peeled off. [Prior Art Literature] [Patent Document]

[Patent Document 1] Patent No. 3594853

[Problem solved by the invention]

In the processing step using the adhesive sheet described in Patent Document 1, an object to be processed using the adhesive sheet (hereinafter also referred to as "object to be processed") is temporarily fixed, and after predetermined processing is applied to the object to be processed, the processed The object is separated from the adhesive sheet. However, particularly in the manufacture of electronic parts and the like, at least one of a step of cutting an object to be processed and a step of grinding is included, and many of them go through a plurality of processing steps. Therefore, for example, for an object to be processed temporarily fixed on an adhesive sheet, after the object to be processed is subjected to at least one of the step of cutting and the step of grinding, the object to be processed is separated from the adhesive sheet, and the separated processing The object is attached to the new adhesive sheet and provided for the next step. In addition, for an object to be processed temporarily fixed on an adhesive sheet, there is also a case where the object to be processed is separated from the adhesive sheet after performing a processing step other than the step of cutting the object to be processed and the step of performing grinding. The object is attached to the new adhesive sheet, and the object to be processed is subjected to at least one processing step of a step of cutting and a step of grinding.

However, when a product is manufactured as described above, not only does the operation become complicated, but it also leads to a decrease in the productivity of the product. Therefore, it is expected to establish a method that not only suppresses the complexity of work, but also improves the productivity of products.

The object of the present invention is to provide an invention that fixes an object to be processed on a support, and after processing the object to be processed, the object to be processed can be easily separated from the support at one time with a weak force, and as The object to be processed separated from the support can be provided in the state of being attached to the adhesive sheet for processing in the next step, and the object to be processed can be processed at least at any time point before and after the object is separated from the support. At least one of cutting and grinding, a method of manufacturing a processed product subjected to at least one of cutting and grinding, and an adhesive laminate used for manufacturing a processed product subjected to at least one of cutting and grinding. [means to solve the problem]

The inventors of the present invention have found that the above-mentioned problems can be solved by a method of manufacturing a processed product, which is a method of manufacturing a processed product subjected to at least one of cutting and grinding using an adhesive laminate having the following characteristics: : It has a base material and an adhesive layer, and any layer has a layer containing thermally expandable particles, a thermally expandable adhesive sheet (I) and an adhesive sheet (II) having a base material and an adhesive layer, wherein the adhesive sheet (I) It is directly laminated with the substrate of the adhesive sheet (II).

That is, the present invention relates to the following [1] to [17]. [1] A method of manufacturing a processed product, which is a method of manufacturing a processed product subjected to at least one of cutting and grinding using an adhesive laminate, wherein the adhesive laminate includes: a substrate (Y1) and an adhesive layer (X1), and a thermally expandable adhesive sheet (I) containing thermally expandable particles having a thermal expansion start temperature (t) in any layer, and an adhesive sheet (II) having a substrate (Y2) and an adhesive layer (X2) ), and it is formed by direct lamination of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), the aforementioned manufacturing method has the following steps (1) to (3) in sequence, Step (1): a step of attaching the surface of the adhesive layer (X1) of the aforementioned adhesive laminate to the support, and attaching an additional object to the surface of the adhesive layer (X2) of the aforementioned adhesive laminate; Step (2): a step of subjecting the aforementioned object to be processed to one or more processes; Step (3): By heating above the thermal expansion start temperature (t) of the thermally expandable particles, while maintaining the state where the object to be processed is attached to the surface of the adhesive layer (X2) of the adhesive laminate, place the The step of separating the aforementioned adhesive laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II); Furthermore, the following step (4) is provided, Step (4): A step of performing at least one of cutting and grinding on the surface of the aforementioned object to be processed which is opposite to the surface to which the adhesive layer (X2) is attached; The aforementioned step (4) is implemented in at least one of the following (X) and (Y), (X): As one or more of the above-mentioned processings, it is implemented in the aforementioned step (2); (Y): implemented after the aforementioned step (3). [2] The production method according to [1], wherein the thermal expansion start temperature (t) of the thermally expandable particles is 60 to 270°C. [3] The production method according to [1] or [2], wherein the substrate (Y1) of the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) containing the aforementioned thermally expandable particles. [4] The production method according to [3], wherein the substrate (Y1) of the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). [5] The production method according to [3] or [4], wherein the heat-expandable base material layer (Y1-1) of the base material (Y1) of the adhesive sheet (I) and the base material of the adhesive sheet (II) (Y2) directly laminated. [6] The production method according to any one of [3] to [5], wherein the adhesive sheet (I) has a substrate ( The composition of Y1), A structure in which the first adhesive layer (X11) of the adhesive sheet (I) is directly laminated to the substrate (Y2) of the adhesive sheet (II), The surface of the second adhesive layer (X12) of the adhesive sheet (I) is attached to the surface of the aforementioned support. [7] The production method according to [1] or [2], wherein the first adhesive layer (X11) is a heat-expandable adhesive layer containing the aforementioned heat-expandable particles, The second adhesive layer (X12) is a non-thermally expandable adhesive layer, A structure in which the first adhesive layer (X11) of the adhesive sheet (I) is directly laminated to the substrate (Y2) of the adhesive sheet (II), The surface of the second adhesive layer (X12) of the adhesive sheet (I) is attached to the surface of the aforementioned support. [8] The production method according to [6] or [7], wherein the surface of the base material (Y1) on which the first adhesive layer (X11) is laminated is a surface that is subjected to an easy-adhesive treatment. [9] The production method according to any one of [1] to [8], wherein the surface of the substrate (Y2) on which the adhesive sheet (I) is laminated is a surface subjected to release treatment. [10] The production method according to any one of [1] to [9], wherein the adhesive sheet (II) has an intermediate layer (Z2) between the substrate (Y2) and the adhesive layer (X2). [11] The production method according to any one of [1] to [10], wherein the adhesive layer (X2) of the adhesive sheet (II) is an energy ray-curable adhesive layer. [12] The production method according to any one of [1] to [11], wherein the adhesive sheet (II) satisfies 1 or more of the following requirements (α) to (γ), ・Requirement (α): The Young's modulus of the substrate (Y2) is 1.0 MPa or more; ・Requirement (β): The thickness of the substrate (Y2) is 5 μm or more; ・Requirement (γ): The storage modulus G' (23°C) of the adhesive layer (X2) is 0.1 MPa or more. [13] The production method according to any one of [1] to [12], wherein the object to be processed is a semiconductor wafer, The aforementioned one or more processes in the aforementioned step (2) include the following step (2-A), Step (2-A): a step of forming a modified region to be a starting point of division on the aforementioned semiconductor wafer; The aforementioned step (4) is the following step (4-A), Step (4-A): a step of grinding the surface of the semiconductor wafer on the opposite side to the sticking surface of the adhesive layer (X2); The aforementioned step (4-A) is implemented in the following (X-A) or (Y-A), (X-A): As one or more of the above-mentioned processes, it is implemented after the above-mentioned step (2-A); (Y-A): implemented after the aforementioned step (3). [14] The production method according to any one of [1] to [12], wherein the object to be processed is a semiconductor wafer, The aforementioned one or more processes in the aforementioned step (2) include the following step (2-B), Step (2-B): Cover the peripheral portion of the aforementioned semiconductor chip and the aforementioned semiconductor chip on the adhesive surface of the adhesive layer (X2) with a packaging material, and harden the packaging material to obtain the aforementioned semiconductor chip packaged in a hardened The step of forming a hardened package from the packaging material; The aforementioned step (4) is implemented in at least one of the following (X-B) and (Y-B), (X-B): As one or more of the above-mentioned processes, it is carried out after the above-mentioned step (2-B); (Y-B): implemented after the aforementioned step (3). [15] The production method according to any one of [1] to [12], wherein the object to be processed is a semiconductor wafer having a modified region serving as a starting point for division, The aforementioned step (4) is the following step (4-A), Step (4-A): A step of grinding the surface of the aforementioned semiconductor wafer opposite to the sticking surface of the adhesive layer (X2). [16] The production method according to any one of [1] to [12], wherein the object to be processed is a semiconductor wafer having an incision groove serving as a starting point for division, The aforementioned step (1) is the following step (1-C), and the aforementioned step (4) is the following step (4-C), Step (1-C): attaching the surface of the adhesive layer (X1) of the aforementioned adhesive laminate to a support, and simultaneously attaching the aforementioned semiconductor wafer to the surface of the adhesive layer (X2) of the aforementioned adhesive laminate It has the step of cutting into the face of the ditch; Step (4-C): A step of grinding the surface of the aforementioned semiconductor wafer opposite to the sticking surface of the adhesive layer (X2). [17] An adhesive laminate for producing a processed product subjected to at least one of cutting and grinding, comprising: a substrate (Y1) and an adhesive layer (X1), and either layer contains heat-expandable particles The heat-expandable adhesive sheet (I), and the adhesive sheet (II) having the base material (Y2) and the adhesive layer (X2), and it is composed of the adhesive sheet (I) and the base material of the adhesive sheet (II) (Y2) directly laminated. [Effect of Invention]

According to the present invention, an object to be processed is fixed to a support, and after the object is processed, the object to be processed can be easily separated from the support at one time with a weak force, and the object can be separated from the support. The object to be processed is attached to the adhesive sheet and provided for processing in the next step, and at least one of cutting and grinding of the object to be processed can be performed at least one of time points before and after separation from the support of the object to be processed A method of manufacturing a processed product subjected to at least one of cutting and grinding, and an adhesive laminate used for manufacturing a processed product subjected to at least one of cutting and grinding.

In this specification, a "layer" means a "non-thermally expandable layer" or a "thermally expandable layer", and it can be judged by the following. The target layer was heat-treated for 3 minutes at the expansion start temperature (t) of the thermally expandable particles contained in the layer containing the thermally expandable particles. When the volume change rate calculated by the following formula is less than 5%, the layer is judged as a "non-thermally expandable layer", and when it is 5% or more, the layer is judged as a "thermally expandable layer". ・Volume change rate (%)={(volume of the aforementioned layer after heat treatment-volume of the aforementioned layer before heat treatment)/volume of the aforementioned layer before heat treatment}×100 In addition, a layer not containing thermally expandable particles is referred to as a "non-thermally expandable layer".

In the present specification, the term "active ingredient" means a component that excludes a diluent solvent among the components contained in the target composition. In the present specification, the mass average molecular weight (Mw) is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC), and is specifically a value measured by the method described in Examples. In this specification, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also the same. In this specification, the lower limit value and the upper limit value described in stages can be independently combined with respect to preferable numerical ranges (for example, ranges such as content). For example, it can be seen from the description of "preferably 10-90, more preferably 30-60", it can be obtained by combining "preferably the lower limit (10)" and "preferably the upper limit (60)" "10~60".

[Manufacturing method of processed products] The method for producing a processed product of the present invention is a method for producing a processed product subjected to at least one of cutting and grinding using an adhesive laminate comprising: a substrate (Y1) and an adhesive layer (X1), and a thermally expandable adhesive sheet (I) containing thermally expandable particles having a thermal expansion start temperature (t) in any layer, and an adhesive sheet (II) having a substrate (Y2) and an adhesive layer (X2) ), and it is formed by direct lamination of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), The aforementioned manufacturing method has the following steps (1) to (3) in sequence, ・Step (1): The step of attaching the surface of the adhesive layer (X1) of the aforementioned adhesive laminate to the support, and attaching an additional object to the surface of the adhesive layer (X2) of the aforementioned adhesive laminate ; ・Step (2): A step of applying one or more processes to the aforementioned object to be processed; ・Step (3): By heating above the thermal expansion start temperature (t) of the thermally expandable particles, while maintaining the state where the object to be processed is attached to the surface of the adhesive layer (X2) of the adhesive laminate, A step of separating the aforementioned adhesive laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II); Furthermore, the following step (4) is provided, ・Step (4): A step of performing at least one of cutting and grinding on the surface of the aforementioned object to be processed which is opposite to the surface to which the adhesive layer (X2) is attached; The aforementioned step (4) is implemented in at least one of the following (X) and (Y), (X): As one or more of the above-mentioned processings, it is implemented in the aforementioned step (2); (Y): implemented after the aforementioned step (3). Hereafter, after demonstrating the adhesive laminate used for the manufacturing method of this invention, each manufacturing process including process (1)-(4) is demonstrated.

[Constitution of Adhesive Laminate] The adhesive laminate used in the production method of the present invention has a base material (Y1) and an adhesive layer (X1), any layer contains heat-expandable particles, and the heat-expandable adhesive sheet (I) has a base material ( The adhesive sheet (II) of Y2) and the adhesive layer (X2), the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) are directly laminated, and are used to apply predetermined processing to the object to be processed Fix the object to be processed on the support body. In this specification, predetermined processing means the processing of the step (2) in the production method of the present invention. Furthermore, in the present invention, step (4) may be implemented as one of one or more processes in step (2). Therefore, the predetermined processing also includes step (4) in the production method of the present invention. In the adhesive laminate used in the production method of the present invention, the surface of the adhesive layer (X1) of the adhesive sheet (I) is the surface on which the support is attached. When the adhesive sheet (I) has the first adhesive layer (X11) and the second adhesive layer (X12), the surface of the second adhesive layer (X12) is the surface on which the support is attached, and the first adhesive layer (X11 ) is the surface laminated on the substrate (Y2) side of the adhesive sheet (II). Also, the surface of the adhesive layer (X2) of the adhesive sheet (II) is the surface on which the object to be processed is attached. On the other hand, the adhesive laminate used in the production method of the present invention can be based on the adhesive sheet (I) and the adhesive sheet (II) by heat treatment at a temperature higher than the expansion start temperature (t) of the heat-expandable particles. The interface P of the material (Y2) is separated. In the following description, this heat treatment is also referred to as "heat treatment for separation". 1 to 3 are schematic cross-sectional views showing the constitution of the adhesive laminates used in the first, second, and third aspects of the production method of the present invention.

＜Adhesive laminate of the first form＞ As an adhesive laminated body used for the 1st aspect of the manufacturing method of this invention, the adhesive laminated body 1a, 1b shown in FIG.1(a), (b) is mentioned, for example. Adhesive laminates 1a and 1b include an adhesive sheet (I) having a substrate (Y1) and an adhesive layer (X1) and an adhesive sheet (II) having a substrate (Y2) and an adhesive layer (X2), and have The substrate (Y1) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) are directly laminated.

The adhesive laminate used in the production method of the present invention is intended to be separated at the interface P by heat treatment for separation, and any layer of the adhesive sheet (I) is used as a layer containing thermally expandable particles. In the adhesive laminate used in the production method of the present invention, the thermally expandable particles are expanded by heat treatment for separation, and unevenness is formed on the surface of the layer containing the thermally expandable particles. Thereby, the contact area of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) decreases. As a result, the object to be processed is pasted on the surface of the adhesive layer (X2) of the adhesive sheet (II), and after predetermined processing is applied, the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) are bonded. ) to separate the interface P to obtain the object to be processed in the state attached to the adhesive sheet (II) to be processed.

Therefore, in the production method of the present invention, the object to be processed can be lifted from the support body once with a weak force while carrying out predetermined processing while fixing the object to be processed on the support body through the above-mentioned adhesive laminate. Easily separates. And the object to be processed separated from the support can be directly provided in the next step in a state of being attached to the adhesive sheet (II). Therefore, the work of attaching the separated object to be processed to the new adhesive sheet becomes unnecessary, and workability and product productivity can be improved.

Regarding the first aspect of the present invention, the base material (Y1) preferably has a heat-expandable base material layer (Y1-1) containing heat-expandable particles such as the adhesive laminates 1a and 1b shown in FIG. 1 . Also, the substrate (Y1) is an adhesive laminate 1a as shown in FIG. 1( a ), and may have a single-layer configuration having only a thermally expandable substrate layer (Y1-1) containing thermally expandable particles. In addition, the substrate (Y1) is an adhesive laminate 1b as shown in Figure 1(b), and may be a composite layer having a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). constitute.

Adhesive laminate 1a shown in Fig. 1(a) is to expand the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) by heat treatment for separation, and the heat-expandable particles on the base material (Y1) The surface of the adhesive sheet (II) side of Y1) has unevenness, which reduces the contact area between the substrate (Y1) and the substrate (Y2) of the adhesive sheet (II). On the other hand, since the adhesive layer (X1) having the adhesive laminate 1a is attached to the support, unevenness is hardly formed on the surface of the substrate (Y1) on the adhesive layer (X1) side. Thereby, unevenness|corrugation can be formed efficiently on the surface of the base material (Y1) connected with the adhesive sheet (II). As a result, the adhesive laminate 1a can be easily separated at one time by applying a weak force to the interface P between the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). Furthermore, it can be designed that the adhesive layer (X1) having the adhesive laminate 1a can be more easily separated at the interface P by forming the self-adhesive composition from the adhesive composition intended to improve the adhesive force to the support.

Also, the adhesive laminate 1b shown in Fig. 1(b) is that the heat-expandable particles contained in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) will expand by heat treatment for separation, and The surface of the substrate (Y1) on the side of the adhesive sheet (II) has unevenness, and the contact area between the substrate (Y1) and the substrate (Y2) of the adhesive sheet (II) decreases. On the other hand, the non-heat-expandable base material layer (Y1-2) constituting the base material (Y1) has a small degree of expansion by heat treatment, so the adhesive layer (X1) side of the base material (Y1) It is difficult to form unevenness on the surface. Thereby, irregularities can be efficiently formed on the surface of the substrate (Y1) on the side of the adhesive sheet (II). As a result, the adhesive laminate 1b can be easily separated by applying a weak force at the interface P between the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). In addition, as in the case of the adhesive laminate 1a, the adhesive layer (X1) included in the adhesive laminate 1b can be designed to be formed of an adhesive composition in order to increase the adhesive force to the support. , it can be more easily separated at the interface P.

In view of the above, for the first aspect of the present invention, the adhesive laminate 1b shown in Figure 1(b), the base material (Y1) has a thermally expandable base material layer (Y1-1 ), preferably with a non-thermally expandable base material layer (Y1-2) on the other surface side.

Also, in the first aspect of the present invention, from the viewpoint of being an adhesive laminate that can be easily separated at one time by applying a weak force to the interface P, in the adhesive laminate 1a, 1b, the adhesive sheet (I It is preferable that the heat-expandable base material layer (Y1-1) of the base material (Y1) and the base material (Y2) of the adhesive sheet (II) are directly laminated.

＜Adhesive laminate of the second aspect＞ As the adhesive laminated body used for the 2nd aspect of the manufacturing method of this invention, the adhesive laminated body 1c, 1d shown to FIG.2(a), (b) is mentioned, for example. In the adhesive laminates 1c and 1d, the adhesive sheet (I) has a structure in which the substrate (Y1) is sandwiched between the first adhesive layer (X11) and the second adhesive layer (X12), and the adhesive sheet (I) The 1st adhesive layer (X11) and the base material (Y2) of the adhesive sheet (II) have the structure of direct lamination. And the surface of the 2nd adhesive layer (X12) becomes the surface which sticks to a support body about adhesive laminated body 1c, 1d.

Regarding the second aspect of the present invention, the base material (Y1) preferably has a heat-expandable base material layer (Y1-1) containing heat-expandable particles, as shown in Fig. 2 as adhesive laminates 1c and 1d. Also, the base material (Y1) is an adhesive laminate 1c as shown in FIG. 2( a ), and may have a single-layer structure of a thermally expandable base material layer (Y1-1) containing thermally expandable particles. In addition, the substrate (Y1) as shown in Figure 2(b) is an adhesive laminate 1d, which may also be a multi-layer with a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). constitute. Also, when the base material (Y1) is a multi-layer structure having a thermally expandable base material layer (Y1-1) and a non-thermally expandable base material layer (Y1-2), the thermally expandable base material layer (Y1-1) is disposed on On the side of the adhesive sheet (II), the non-heat-expandable base material layer (Y1-2) is preferably arranged on the side of the second adhesive layer (X12).

Adhesive laminated body 1c shown in Fig. 2 (a) is that by heat treatment for separation, the heat-expandable particles in the heat-expandable base material layer (Y1-1) constituting the base material (Y1) are expanded and deposited on the base material (Y1-1). The surface of Y1) on the side of the first adhesive layer (X11) has irregularities. The first adhesive layer (X11) can also be pushed up by the unevenness produced on the surface of the substrate (Y1), and the surface of the adhesive sheet (II) side of the first adhesive layer (X11) can also be pushed up. Form bumps. Thereby, the contact area of the 1st adhesive layer (X11) and the base material (Y2) of the adhesive sheet (II) decreases. On the other hand, since the support was attached to the second adhesive layer (X12), unevenness was hardly formed on the surface of the substrate (Y1) on the second adhesive layer (X12) side. Therefore, unevenness can be efficiently formed on the surface of the substrate (Y1) on the side of the first adhesive layer (X11), and unevenness can be efficiently formed on the surface of the adhesive sheet (II) of the first adhesive layer (X11). . As a result, in the adhesive laminate 1c, the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) can be easily separated at one time with weak force. . In addition, when the second adhesive layer (X12) of the adhesive laminate 1c is formed of an adhesive composition to improve the adhesive force to the support, it can be more easily formed at the interface P. separate.

Moreover, the adhesive laminated body 1d shown in FIG. 2(b) expands the heat-expandable particle|grains contained in the heat-expandable base material layer (Y1-1) which comprises base material (Y1) by heat-processing for separation, and is based on The surface of the material (Y1) on the side of the first adhesive layer (X11) has irregularities. The first adhesive layer (X11) is also pressed by the unevenness generated on the surface of the substrate (Y1), and unevenness is also formed on the surface of the first adhesive layer (X11) on the adhesive sheet (II) side. Thereby, the contact area of the 1st adhesive layer (X11) and the base material (Y2) of the adhesive sheet (II) decreases. On the other hand, the non-heat-expandable base material layer (Y1-2) constituting the base material (Y1) can reduce the degree of expansion by heat treatment, so the second adhesive layer (X12) of the base material (Y1) It is difficult to form unevenness on the side surface. Accordingly, unevenness can be efficiently formed on the surface of the substrate (Y1) on the side of the first adhesive layer (X11). As a result, in the adhesive laminate 1d, the interface P between the base material (Y1) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) can be easily separated at one time with weak force. Also, in the same manner as in the case of the adhesive laminate 1c, the second adhesive layer (X12) of the adhesive laminate 1d may be designed to use an adhesive composition to improve the adhesive force to the support. Formed, the interface P can be more easily separated.

Among them, regarding the second aspect of the present invention, from the viewpoint of being an adhesive laminate that can be easily separated at one time also at the interface P with a weak force, in the adhesive laminate 1c, 1d, the adhesive sheet (I) has It is preferable that the thermally expandable base material layer (Y1-1) of the base material (Y1) and the first adhesive layer (X11) are directly laminated. In this case, it is more preferable that the 1st adhesive layer (X11) and the base material (Y2) of the sheet|seat (II) for resin film formation are laminated|stacked directly.

＜Adhesive laminate of the third aspect＞ In the adhesive laminates 1a and 1b of the first aspect of the production method of the present invention, and the adhesive laminates 1c and 1d of the second aspect, the substrate (Y1) is used as one of the layers comprising Those with a layer of heat-expandable particles. On the other hand, as the adhesive laminate used in the third aspect of the production method of the present invention, on the surface of the interface P side of the substrate (Y1) of the adhesive sheet (I), a layer containing the aforementioned thermally expandable particles is provided. The heat-expandable adhesive layer may be provided with a non-heat-expandable adhesive layer on the other surface of the substrate (Y1). As such an aspect, for example, in the adhesive laminate 2 shown in FIG. 3 , the adhesive sheet (I) has a substrate sandwiched by the first adhesive layer (X11) and the second adhesive layer (X12). In the composition of (Y1), the first adhesive layer (X11) is a thermally expandable adhesive layer containing thermally expandable particles, the second adhesive layer (X12) is a non-thermally expandable adhesive layer, and the second adhesive sheet (I) is provided. 1 A configuration in which the adhesive layer (X11) is directly laminated to the base material (Y2) of the adhesive sheet (II). And, the surface of the 2nd adhesive layer (X12) is the sticking surface with a support body about the said structure like the adhesive laminated body 2. Moreover, in the above-mentioned structure like the adhesive laminate 2, it is preferable that the base material (Y1) is a non-heat-expandable base material.

With regard to the adhesive laminate 2 shown in FIG. 3, unevenness is produced on the surface of the heat-expandable adhesive layer of the first adhesive layer (X11) by heat treatment for separation, and the first adhesive layer (X11) and the adhesive sheet (II) The contact area of the substrate (Y2) is reduced. On the other hand, since the base material (Y1) side surface of the first adhesive layer (X11) is laminated with the base material (Y1) which is not a heat-expandable base material, unevenness hardly occurs. Therefore, irregularities can be efficiently formed on the surface of the first adhesive layer (X11) on the side of the adhesive sheet (II). As a result, the adhesive laminate 2 can be easily separated with weak force at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II).

<Constitution of Adhesive Laminate with Release Material> In the adhesive laminate used in one aspect of the production method of the present invention, either the surface of the adhesive layer (X1) to which the support is attached or the surface of the adhesive layer (X2) to which the object to be processed is attached or On both sides, it can further be made into the structure which laminated|stacked the peeling material. Also, for example, for the adhesive laminates 1a and 1b shown in Figure 1(a), (b), on the adhesive surface of one side of the adhesive layer (X1) and the adhesive layer (X2), peeling will be applied to both sides. When the treated release material is to be laminated, it can be rolled into a roll configuration. Adhesive laminates 1c and 1d shown in Fig. 2(a) and (b) and adhesive laminate 2 shown in Fig. 3 can also be rolled into rolls in the same way.

[Physical properties of the adhesive laminate] The adhesive laminate used in one aspect of the production method of the present invention is heated on the adhesive sheet ( The interface P between I) and the base material (Y2) of the adhesive sheet (II) can be easily separated at one time with weak force. Among them, in the adhesive laminate according to one aspect of the present invention, the peeling force (F ₁ ), usually 0-2000mN/25mm, preferably 0-1000mN/25mm, more preferably 0-150mN/25mm, more preferably 0-100mN/25mm, more preferably 0-50mN/25mm. And when the peeling force (F ₁ ) is 0 mN/25mm, even when the peeling force is measured by the method described in the examples, the peeling force may be too small to contain and may not be measured.

Also, from the viewpoint of sufficiently fixing the object to be processed without adversely affecting the processing operation before heat treatment, the interlayer adhesion between the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) Those with higher sex are better. In view of the above, for the adhesive laminate used in one aspect of the production method of the present invention, the peeling force (F ₀ ) at the time of separation at the interface P before heat treatment is 100 mN/25 mm or more. Better, preferably more than 300mN/25mm, more preferably more than 500mN/25mm, and more preferably less than 50000mN/25mm.

In one aspect of the adhesive laminate used in the production method of the present invention, the peeling force (F ₀ ) is larger than the peeling force (F ₁ ). Specifically, the ratio [(F ₁ )/(F ₀ )] of peeling force (F ₁ ) to peeling force (F ₀ ) is preferably 0-0.9, more preferably 0-0.8, more preferably 0-0.5 , more preferably 0 to 0.2.

In addition, the temperature conditions for measuring the peeling force (F ₁ ) may be not less than the expansion start temperature (t) and the temperature at which the heat-expandable particles are expanded. Moreover, as temperature conditions at the time of measuring the peeling force (F ₀ ), it is only required to be less than the expansion start temperature (t), and it is basically room temperature (23° C.). However, more specific measurement conditions and measurement methods of the peeling force (F ₁ ) and the peeling force (F ₀ ) are based on the methods described in the examples.

Regarding the adhesive laminate used in one aspect of the production method of the present invention, at room temperature (23°C), the adhesive layer (X1) (the first adhesive layer (X11) as the adhesive sheet (I) and the second adhesive layer (X12)) and the adhesive force of the adhesive layer (X2) of the adhesive sheet (II) are independently preferably 0.1 to 10.0 N/25mm, more preferably 0.2 to 8.0 N/25mm, more preferably 0.4-6.0N/25mm, more preferably 0.5-4.0N/25mm. When the adhesive sheet (I) has the first adhesive layer (X11) and the second adhesive layer (X12), the adhesive forces of the first adhesive layer (X11) and the second adhesive layer (X12) are each in the above range Preferably, the second adhesive layer (X12) attached to the support has a stronger adhesive force than the first adhesive layer from the viewpoint of improving the adhesion with the support and allowing easier separation at the interface P. The layer (X11) with higher adhesion is preferred.

The substrate (Y1) included in the adhesive sheet (I) and the substrate (Y2) included in the adhesive sheet (II) are non-adhesive substrates. In the present invention, whether or not it is a non-adhesive base material is judged as if the probe viscosity value measured in accordance with JIS Z0237: 1991 is less than 50mN/5mmφ on the surface of the target base material. The material is "non-adhesive substrate". The probe viscosity values in the surface of the substrate (Y1) of the adhesive sheet (I) used in one aspect of the present invention and the substrate (Y2) of the adhesive sheet (II) are independent of each other. It is less than 50mN/5mmφ, preferably less than 30mN/5mmφ, more preferably less than 10mN/5mmφ, more preferably less than 5mN/5mmφ. Also, in this specification, the specific measurement method of the probe viscosity value on the surface of the heat-expandable substrate is based on the method described in the examples.

Each layer constituting the adhesive laminate of the present invention will be described below.

[Construction of Adhesive Sheet (I)] The adhesive sheet (I) of the adhesive laminate used in the production method of the present invention has a base material (Y1) and an adhesive layer (X1), and is intended to be separated from the adhesive sheet (II) by heat treatment. The interface of the substrate (Y2) is separated, which is a heat-expandable adhesive sheet containing heat-expandable particles in any layer. In one aspect of the present invention, the thermal expansion initiation temperature (t) of the heat-expandable particles is preferably 60-270°C.

As the adhesive sheet (I) used in one aspect of the present invention, the following aspects are preferable. ・Adhesive sheet (I) of the first aspect: The substrate (Y1) is an adhesive sheet (I) having a thermally expandable substrate layer (Y1-1) containing thermally expandable particles. ・Adhesive sheet (I) of the second aspect: On both sides of the substrate (Y1), between the first adhesive layer (X11) having a heat-expandable adhesive layer containing heat-expandable particles and the non-heat-expandable adhesive layer Adhesive sheet (I) of the second adhesive layer (X12). ・The substrate (Y1) is an adhesive sheet (I) that is a non-thermally expandable substrate. The adhesive sheet (I) of the 1st aspect and the 2nd aspect used in one aspect of this invention is demonstrated below.

＜Adhesive sheet of the first form (I)＞ As the adhesive sheet (I) of the first aspect, as shown in Figs. 1 and 2 , a substrate (Y1) having a thermally expandable substrate layer (Y1-1) containing thermally expandable particles can be mentioned.

Regarding the adhesive sheet (I) of the first aspect, the adhesive layer ( X1) A non-heat-expandable adhesive layer is preferred. Specifically, for the adhesive sheet (I) included in the adhesive laminates 1a and 1b shown in FIG. 1 , the adhesive layer (X1) is preferably a non-thermally expandable adhesive layer. Also, for the adhesive sheet (I) included in the adhesive laminates 1c and 1d shown in FIG. Layers are better.

The thickness of the base material (Y1) before heat treatment for separating the adhesive sheet (I) of the first aspect is preferably 10-1000 μm, more preferably 20-700 μm, more preferably 25-500 μm, more preferably 30 ~300μm.

The thickness of the adhesive layer (X1) before heat treatment for separation of the adhesive sheet (I) of the first aspect is preferably 1-60 μm, more preferably 2-50 μm, more preferably 3-40 μm, still more preferably 5 to 30 μm.

And, for this specification, for example, as shown in FIG. 2, when the adhesive sheet (I) has a plurality of adhesive layers, the above-mentioned "thickness of the adhesive layer (X1)" means the thickness of each adhesive layer (in FIG. 2 where each is the thickness of the adhesive layer (X11) and (X12)). In addition, in this specification, the thickness of each layer which comprises an adhesive laminated body shows the value measured by the method described in an Example.

For the adhesive sheet (I) of the first aspect, before heat treatment for separation, as the thickness ratio of the thermally expandable base material layer (Y1-1) to the adhesive layer (X1) [(Y1-1)/(X1 )], preferably less than 1000, more preferably less than 200, more preferably less than 60, more preferably less than 30. If the thickness ratio is 1000 or less, an adhesive laminate can be easily separated at one time with weak force at the interface P of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) by heat treatment. . In addition, the thickness ratio is preferably at least 0.2, more preferably at least 0.5, more preferably at least 1.0, and still more preferably at least 5.0.

Also, in the adhesive sheet (I) of the first aspect, the base material (Y1) as shown in Figure 1(a), may also be composed only of a heat-expandable base material layer (Y1-1), as shown in Figure 1(a). 1(b) may have a heat-expandable base material layer (Y1-1) on the adhesive sheet (II) side and a non-heat-expandable base material layer (Y1-2) on the adhesive layer (X1) side.

For the adhesive sheet (I) of the first aspect, before heat treatment for separation, as the thickness ratio of the heat-expandable base material layer (Y1-1) to the non-heat-expandable base material layer (Y1-2) [(Y1- 1)/(Y1-2)], preferably 0.02-200, more preferably 0.03-150, more preferably 0.05-100.

＜Adhesive sheet of the second aspect (I)＞ As the adhesive sheet (I) of the second aspect, as shown in FIG. 3 , the first adhesive layer ( X11), and the second adhesive layer (X12) having a non-heat-expandable adhesive layer. And, in the adhesive sheet (I) of the second aspect, the first adhesive layer (X11) of the heat-expandable adhesive layer is in direct contact with the base material (Y2) of the adhesive sheet (II). And, for the adhesive sheet (I) of the second aspect, the substrate (Y1) is preferably a non-thermally expandable substrate layer.

For the adhesive sheet (I) of the second aspect, before heat treatment for separation, the first adhesive layer (X11) as the thermally expandable adhesive layer and the second adhesive layer (X12) as the non-thermally expandable adhesive layer ) thickness ratio [(X11)/(X12)] is preferably 0.1-80, more preferably 0.3-50, more preferably 0.5-15.

Also, for the adhesive sheet (I) of the second aspect, before heat treatment for separation, the thickness ratio of the first adhesive layer (X11) as the heat-expandable adhesive layer to the substrate (Y1) [(X11) /(Y1)], preferably 0.05-20, more preferably 0.1-10, more preferably 0.2-3.

The heat-expandable particles contained in any layer constituting the adhesive sheet (I) are described below. The heat-expandable base material layer (Y1-1) and the non-heat-expandable base material layer (Y1-2) constituting the base material (Y1) and the adhesive layer (X1) will be described in detail.

＜Heat-expandable particles＞ The heat-expandable particles used in the present invention are only those that can be expanded by heating, but those whose expansion start temperature (t) is adjusted to 60-270°C are preferable. The expansion start temperature (t) is appropriately selected according to the application of the adhesive laminate. For example, in the manufacturing method of the present invention, in step (1) and step (2), when the adhesive laminate is exposed to high temperature environment (for example, when performing a process of forming a modified region as a division starting point inside a semiconductor wafer) etc.), the expansion start temperature of the heat-expandable particles is preferably within the above temperature range and as low as possible. Thereby, the heating energy required for separating the adhesive sheet (I) and the adhesive sheet (1I) is set to be smaller, which can reduce the manufacturing cost of cutting and/or grinding objects. Also, the adhesive sheet (I) and the adhesive sheet (1I) can be separated without going through the excess heat history of the object to be processed. In this specification, the expansion start temperature (t) of a heat-expandable particle shows the value measured by the following method.

(Measurement method of expansion start temperature (t) of heat-expandable particles) In an aluminum cup with a diameter of 6.0mm (inner diameter 5.65mm) and a depth of 4.8mm, add 0.5mg of heat-expandable particles to be measured, and cover the top with an aluminum lid (diameter 5.6mm, thickness 0.1mm) to prepare a sample . Using a dynamic viscoelasticity measuring device, the height of the sample was measured in a state where a force of 0.01 N was applied from the upper part of the aluminum cover with a potentiostat. Then, under the state of applying a force of 0.01N by the potentiostat, heat it at a temperature increase rate of 10°C/min from 20°C to 300°C, measure the displacement in the vertical direction of the potentiostat, and align the positive The starting temperature of the displacement of the direction is taken as the expansion starting temperature (t).

The heat-expandable particles are preferably microencapsulated foaming agents composed of a shell made of a thermoplastic resin, and a contained component enclosed in the shell and vaporized when heated to a predetermined temperature. Examples of the thermoplastic resin constituting the shell of the microencapsulated blowing agent include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polypropylene Nitrile, Polyvinylidene Chloride, Polyethylene, etc.

Examples of the contained components contained in the shell include propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentane, isohexane, and isoheptane. alkanes, isooctane, isononane, isodecane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, neopentane, dodecane, isododecane, Cyclotridecane, Hexylcyclohexane, Tridecane, Tetradecane, Pentadecane, Hexadecane, Heptadecane, Octadecane, Nonadecane, Isotridecane, 4-Methyldodecane , Isotetradecane, Isopentadecane, Isohexadecane, 2,2,4,4,6,8,8-Heptamethylnonane, Isoheptadecane, Isoctadecane, Isnonadecane , 2,6,10,14-tetramethylpentadecane, cyclotridecane, heptylcyclohexane, n-octylcyclohexane, cyclopentadecane, nonylcyclohexane, decylcyclohexane alkane, pentadecylcyclohexane, hexadecylcyclohexane, heptadecylcyclohexane, octadecylcyclohexane, etc. These inclusion components may be used alone or in combination of two or more. The expansion start temperature (t) of the heat-expandable particles can be adjusted by appropriately selecting the type of the contained component.

The average particle diameter before expansion of the heat-expandable particles used in one aspect of the present invention at 23°C is preferably 3-100 μm, more preferably 4-70 μm, more preferably 6-60 μm, still more preferably 10 ~50 μm. And, the average particle diameter before the expansion of so-called heat-expandable particle, represent volume median particle diameter (D ₅₀ ), use laser diffraction type particle size distribution measuring device (for example the product name " Mastersizer 3000 " manufactured by Malvern company) to measure, for The particle distribution of the heat-expandable particles before expansion means that the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion corresponds to 50% of the particle diameter.

The 90% particle diameter (D ₉₀ ) before expansion at 23°C of the thermally expandable particles used in one aspect of the present invention is preferably 10 to 150 μm, more preferably 20 to 100 μm, more preferably 25 to 90 μm , more preferably 30-80 μm. In addition, the 90% particle diameter (D ₉₀ ) of the heat-expandable particles before expansion means that the heat-expandable particles before expansion are measured using a laser diffraction particle size distribution analyzer (for example, a product name "Mastersizer 3000" manufactured by Malvern Co., Ltd.). In the particle distribution, the cumulative volume frequency calculated from the smaller particle diameter of the heat-expandable particles before expansion is equivalent to 90% of the particle diameter.

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

<Heat-expandable base material layer (Y1-1)> In the adhesive laminate according to one aspect of the present invention, the base material (Y1) of the adhesive sheet (I) has a heat-expandable base material layer (Y1-1) containing heat-expandable particles. In the case of -1), it is preferable that the heat-expandable base material layer (Y1-1) satisfies the following requirement (1).・Requirement (1): The storage modulus E'(t) of the heat-expandable base material layer (Y1-1) is 1.0×10 ⁷ Pa or less at the expansion start temperature (t) of the heat-expandable particles. In addition, in this specification, the storage modulus E' of the thermally expandable base material layer (Y1-1) in predetermined temperature shows the value measured by the method as described in an Example.

The above requirement (1) is an index showing the rigidity of the heat-expandable base material layer (Y1-1) before the heat-expandable particles are expanded. Before the expansion of the heat-expandable particles, the storage modulus E' of the heat-expandable base material layer (Y1-1) decreases as the temperature rises. However, before and after reaching the expansion start temperature (t) of the heat-expandable particles, the decrease in the storage modulus E' of the heat-expandable base material layer (Y1-1) is suppressed because the heat-expandable particles start to expand. On the other hand, since the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) can be easily separated with a weak force, heating to a temperature above the expansion start temperature (t) can Concavity and convexity must be easily formed on the surface of the side laminated with the base material (Y2) of the adhesive sheet (I). In other words, the heat-expandable substrate layer (Y1-1) that satisfies the above requirement (1) expands at the expansion start temperature (t) and the heat-expandable particles become sufficiently large to be bonded to the substrate (Y2) of the adhesive sheet (II). Concavities and convexities are easily formed on the surface of the adhesive sheet (I) on the laminated side. As a result, at the interface P of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II), an adhesive laminate can be easily separated at one time with a weak force.

The storage modulus E'(t) stipulated in the requirement (1) of the thermally expandable base material layer (Y1-1) used in the present invention is preferably 9.0×10 ⁶ Pa or less from the above viewpoint, more preferably It is 8.0×10 ⁶ Pa or less, more preferably 6.0×10 ⁶ Pa or less, still more preferably 4.0×10 ⁶ Pa or less. Also, by suppressing the flow of the expanded heat-expandable particles, the shape retention of the irregularities formed on the surface of the adhesive sheet (I) on the side laminated with the base material (Y2) of the adhesive sheet (II) is improved, and at the interface P From the viewpoint of being easily separated by a weak force, the storage modulus E'(t) stipulated in the requirement (1) of the thermally expandable base material layer (Y1-1) is preferably 1.0×10 ³ Pa or more, and is better than It is preferably at least 1.0×10 ⁴ Pa, more preferably at least 1.0×10 ⁵ Pa.

From the viewpoint of the heat-expandable base material layer (Y1-1) satisfying the above-mentioned requirement (1), the content of the heat-expandable particles in the heat-expandable base material layer (Y1-1) has a significant effect on the heat-expandable base material layer (Y1- 1 to 40 mass % of the total mass (100 mass %) of 1), More preferably, it is 5 to 35 mass %, More preferably, it is 10 to 30 mass %, More preferably, it is 15 to 25 mass %.

Furthermore, from the viewpoint of improving the interlayer adhesion of other layers laminated on the heat-expandable base material layer (Y1-1), the surface of the heat-expandable base material layer (Y1-1) may also be given Surface treatment such as oxidation or embossing, easy-adhesive treatment, or primer treatment. Examples of oxidation methods include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet method), hot air treatment, ozone and ultraviolet irradiation treatment, etc., and examples of roughening methods include sand blasting, solvent treatment, etc. treatment, etc.

The heat-expandable base material layer (Y1-1) is preferably formed of a resin composition (y) containing a resin and heat-expandable particles. And in the resin composition (y), the additive for base materials can be contained as needed in the range which does not impair the effect of this invention. Examples of additives for substrates include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, colorants, and the like. In addition, each of these base material additives may be used independently, or may use 2 or more types together. When these base material additives are contained, the content of each base material additive 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 thermally expandable particles contained in the resin composition (y) of the forming material of the thermally expandable base material layer (Y1-1) are as described above. The content of the heat-expandable particles is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, more preferably 10 to 30% by mass based on the total amount (100% by mass) of active ingredients of the resin composition (y). % by mass, more preferably 15 to 25% by mass.

The resin contained in the resin composition (y) as a forming material of the thermally expandable base material layer (Y1-1) may be a non-adhesive resin or an adhesive resin. In other words, even if the resin contained in the resin composition (y) is an adhesive resin, for the process of forming the thermally expandable base material layer (Y1-1) from the resin composition (y), the adhesive resin and the polymerizable compound are carried out. Polymerization reaction, the obtained resin becomes a non-adhesive resin, and the heat-expandable base material layer (Y1-1) containing this resin only needs to become non-adhesive.

The mass average molecular weight (Mw) of the resin contained in the resin composition (y) is preferably from 10 million to 1 million, more preferably from 10 million to 700,000, more preferably from 10 million 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 any of a block copolymer, a random copolymer, and a graft copolymer.

The content of the resin is preferably 50 to 99 mass %, preferably 60 to 95 mass %, more preferably 65 to 90 mass %, based on the total amount (100 mass %) of the active ingredients of the resin composition (y). , more preferably 70 to 85% by mass.

In addition, from the viewpoint of forming a thermally expandable base material layer (Y1-1) satisfying the above-mentioned requirement (1), as the aforementioned resin contained in the resin composition (y), a resin selected from the group consisting of acrylic urethane-based resins And one or more kinds of olefin-based resins are preferable. Moreover, the following resin (U1) is preferable as said urethane acrylate resin. ・Acrylic urethane resin (U1) made by polymerizing urethane prepolymer (UP) and vinyl compound containing (meth)acrylate.

(Acrylic Urethane Resin (U1)) As the urethane prepolymer (UP) serving as the main chain of the urethane acrylate resin (U1), a reaction product of a polyhydric alcohol and a polyvalent isocyanate is mentioned. Furthermore, it is preferable that the urethane prepolymer (UP) is obtained by performing a chain extension reaction using a chain extender.

Examples of polyols used as raw materials for urethane prepolymers (UP) include alkylene-type polyols, ether-type polyols, ester-type polyols, esteramide-type polyols, ester-ether Type polyols, carbonate type polyols, etc. These polyols may be used alone or in combination of two or more. As the polyhydric alcohol used in one aspect of the present invention, diols are preferred, ester diols, alkylene diols and carbonate diols are preferred, ester diols, carbonate diols Diols are more preferred.

Examples of ester diols include those selected from 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, etc. Alkanediol; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and other alkanediols; one or more kinds of diols, and selected from phthalic acid, isophthalic acid, terephthalic acid Formic acid, naphthalene dicarboxylic acid, 4,4-diphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, chlorendic acid , maleic acid, fumaric acid, itaconic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid , dicarboxylic acids such as hexahydroterephthalic acid and methylhexahydrophthalic acid, and polycondensates of one or more of these anhydrous substances. Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene adipate diol, poly Pentyl adipate, polyethylene propylene adipate, polyethylene butyl adipate, polybutylene hexexylene adipate, polydiethylene ethylene adipate Acid diol, poly(tetramethylene ether) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate Diol, polybutene azelate diol, polybutene sebacate diol, polyethylene neopentyl terephthalate diol, and the like.

Examples of alkylene diols include 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 polytetramethylene glycol; Polyoxyalkylene glycols such as polytetramethylene glycol Alcohol etc.

Examples of carbonate diols include 1,4-tetramethylene carbonate diol, 1,5-pentamethylene carbonate diol, 1,6-hexamethylene carbonate diol, 1,2-Propyl carbonate diol, 1,3-Propylene carbonate diol, 2,2-Dimethyl propylene carbonate diol, 1,7-Heptaethylene carbonate diol Alcohol, 1,8-octylene carbonate diol, 1,4-cyclohexane carbonate diol, etc.

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

Among them, as the polyvalent isocyanate used in one aspect of the present invention, diisocyanate is preferable, and is selected from 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate ( One or more of 2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI) and alicyclic diisocyanate are preferable.

Examples of the alicyclic diisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, etc. Erone diisocyanate (IPDI) is preferred.

Regarding one aspect of the present invention, as the urethane prepolymer (UP) which becomes the main chain of the urethane acrylate resin (U1), it is a reactant of a diol and a diisocyanate to be used in A linear urethane prepolymer having ethylenically unsaturated groups at both terminals is preferable. As a method for introducing ethylenically unsaturated groups at both ends of the linear urethane prepolymer, a linear urethane prepolymer obtained by reacting a diol with a diisocyanate compound is mentioned. The method of reacting the NCO group at the terminal end with hydroxyalkyl (meth)acrylate.

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

As a vinyl compound used as a side chain of the urethane acrylate resin (U1), at least (meth)acrylate is contained. As the (meth)acrylate, one or more selected from alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate is preferred, and alkyl (meth)acrylate and hydroxyalkyl ( Meth)acrylate is preferred.

When using an alkyl (meth)acrylate and a hydroxyalkyl (meth)acrylate together, with respect to 100 parts by mass of the alkyl (meth)acrylate, as the compounding ratio of the hydroxyalkyl (meth)acrylate, Preferably, it is 0.1-100 mass parts, More preferably, it is 0.5-30 mass parts, More preferably, it is 1.0-20 mass parts, More preferably, it is 1.5-10 mass parts.

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

In addition, examples of the hydroxyalkyl (meth)acrylates include hydroxyalkyl (meth)acrylates used for ethylenically unsaturated groups introduced at both ends of the linear urethane prepolymer. Acrylics are the same.

Vinyl compounds other than (meth)acrylates include, for example, aromatic hydrocarbon-based vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methyl vinyl ether, ethyl vinyl ether and other vinyl ethers; vinyl acetate, vinyl propionate, (meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, methyl Polar groups such as (acrylamide) contain monomers and the like. These may be used individually or in combination of 2 or more types.

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

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

The acrylic urethane resin (U1) used in one aspect of the present invention is composed of a mixed urethane prepolymer (UP) and a vinyl compound containing (meth)acrylate. obtained by aggregation. This polymerization is preferably performed by further adding a radical initiator.

Regarding the urethane acrylic resin (U1) used in one aspect of the present invention, as 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)] is preferably 10/90 to 80/20 in mass ratio, more preferably 20/80 to 70/30, more preferably 30/70 to 60/40, more preferably 35/65-55/45.

(Olefin resin) A preferable olefin-based resin as the resin contained in the resin composition (y) is a polymer having at least a constituent unit derived from an olefin monomer. The above-mentioned olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, and specific examples thereof include ethylene, propylene, butylene, isobutylene, and 1-hexene. Among these, ethylene and propylidene groups are also preferred.

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

In one aspect of the present invention, the olefin-based resin can be further modified by one or more kinds of acid-modified, hydroxyl-modified, and acrylic-modified modified olefin-based resins.

For example, acid-modified olefin-based resins obtained by subjecting olefin-based resins to acid modification include those obtained by graft-polymerizing unsaturated carboxylic acids or their anhydrous substances to the above-mentioned unmodified olefin-based resins. modified polymers. Examples of the unsaturated carboxylic acid or its anhydrous product include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutamic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, Maleic anhydride, itaconic anhydride, glutamic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc. Moreover, an unsaturated carboxylic acid or its anhydrate may be used individually, and may use 2 or more types together.

Examples of acrylic-modified olefin-based resins obtained by modifying olefin-based resins with acrylic acid include alkyl (meth)acrylates as side chains on the above-mentioned non-modified olefin-based resins in the main chain. Modified polymer made by graft polymerization. As carbon number of the alkyl group which the said alkyl (meth)acrylate has, 1-20 are preferable, 1-16 are more preferable, and 1-12 are more preferable. Examples of the above-mentioned alkyl (meth)acrylates include the same compounds that can be selected as the monomer (a1') described later.

Examples of hydroxyl-modified olefin-based resins obtained by modifying olefin-based resins with hydroxyl groups include those obtained by graft-polymerizing the above-mentioned non-modified olefin-based resins as the main chain. polymer. Examples of the compound containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as butyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol, allyl Alcohols and other unsaturated alcohols.

(Acrylic urethane resins and resins other than olefin resins) In one aspect of the present invention, the resin composition (y) may contain resins other than the urethane-acrylic resin and the olefin-based resin within the range that does not impair the effect of the present invention. Such resins include, for example, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; polyethylene terephthalate, polybutylene terephthalate, Polyester resins such as polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; Polyurethane; Polyurethane; Polyether ether ketone; Polymer; Polyphenylene sulfide; Polyether imide, polyimide and other polyimide resins; Polyamide resins; Acrylic resin; Fluorine resin, etc.

However, from the viewpoint of forming a thermally expandable base material layer (Y1-1) satisfying the above requirement (1), the difference between the urethane-acrylic resin and the resin other than the olefin-based resin in the resin composition (y) The content ratio is preferably less. As the content ratio of the resin other than the urethane-acrylic resin and the olefin-based resin, it is preferably less than 30 parts by mass with respect to 100 parts by mass of the total amount of the resin contained in the resin composition (y). , preferably less than 20 parts by mass, more preferably less than 10 parts by mass, more preferably less than 5 parts by mass, more preferably less than 1 part by mass.

(Solvent-free resin composition (y1)) As one aspect of the resin composition (y) used in one aspect of the present invention, an oligomer having an ethylenically unsaturated group having a mass average molecular weight (Mw) of 50,000 or less, an energy ray polymerizable monomer A solvent-free resin composition (y1) in which no solvent is added can be exemplified. In the non-solvent type resin composition (y1), although no solvent is added, the energy ray polymerizable monomer is what imparts and improves the plasticity of the said oligomer. A thermally expandable base material layer (Y1-1) satisfying the above requirement (1) can be easily formed by irradiating a coating film formed of the solvent-free resin composition (y1) with energy rays.

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

The mass average molecular weight (Mw) of the aforementioned 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, more preferably 3,000 to 35,000, more preferably More preferably, it is 4,000 to 30,000.

In addition, as the aforementioned oligomer, any resin contained in the aforementioned resin composition (y) may have an ethylenically unsaturated group having a mass average molecular weight of 50,000 or less, but the aforementioned urethane prepolymer (UP) is preferred. In addition, as the oligomer, a modified olefin-based resin having an ethylenically unsaturated group can also be used.

The total content of the aforementioned oligomers and energy ray polymerizable monomers in the solvent-free resin composition (y1) ranges from 50 to 99 mass % is preferable, 60-95 mass % is more preferable, 65-90 mass % is more preferable, 70-85 mass % is still more preferable.

Examples of energy ray polymerizable monomers include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl oxide Alicyclic polymeric compounds such as base (meth)acrylate, cyclohexyl (meth)acrylate, adamantane (meth)acrylate, tricyclodecane acrylate; phenyl hydroxypropyl acrylate, benzyl Aromatic polymeric compounds such as acrylate, phenolic ethylene oxide modified acrylate; tetrahydrofurfuryl (meth)acrylate, morpholine acrylate, N-vinylpyrrolidone, N-vinylhexyl Heterocyclic polymerizable compounds such as amides, etc. These energy ray polymerizable monomers may be used alone or in combination of two or more.

The content ratio [oligomer/energy ray polymerizable monomer] of the aforementioned oligomer and the aforementioned energy ray polymerizable monomer in the solvent-free resin composition (y1) is 20/80～ 90/10 is better, more preferably 30/70-85/15, more preferably 35/65-80/20.

In one aspect of the present invention, it is preferable that a photopolymerization initiator is further added to the solvent-free resin composition (y1). By containing the photopolymerization initiator, the hardening reaction can sufficiently proceed even by irradiation with relatively low-energy energy rays.

Examples of photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzyl phenyl sulfide, tetramethyl Thiuram monosulfide, azobisisobutyronitrile, benzhydryl, diacetyl, 8-chloroanthraquinone, etc. These photopolymerization initiators may be used alone or in combination of two or more.

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

＜Non-heat-expandable base material layer (Y1-2)＞ As the forming material of the non-thermally expandable base material layer (Y1-2) of the constituent material (Y1), for example, paper, resin, metal, etc. can be mentioned, and it can be used in accordance with the application of the adhesive laminate of one aspect of the present invention. Appropriate choice.

Examples of paper materials include thin paper, medium paper, high-quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, cellophane, and the like. As the resin, for example, polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyester resins; polystyrene; acrylonitrile-butadiene-styrene copolymer cellulose triacetate; polycarbonate; polyurethane, acrylic modified polyurethane and other urethane resins; polymethylpentene; polysulfone; polyether ether ketone; poly Ether resin; polyphenylene sulfide; polyimide-based resins such as polyetherimide and polyimide; polyamide-based resins; acrylic resins; fluorine-based resins, etc. As a metal, aluminum, tin, chromium, titanium etc. are mentioned, for example.

These formation materials may consist of 1 type, and may use 2 or more types together. As the non-heat-expandable base material layer (Y1-2) using two or more kinds of forming materials in combination, the paper material is laminated with a thermoplastic resin such as polyethylene, or on the surface of a resin film or sheet containing a resin. Those who form a metal film on it, etc. In addition, as a method of forming the metal layer, for example, a method of vapor-depositing the above-mentioned metal by a PVD method such as vacuum deposition, sputtering, and ion plating, or using a general adhesive on a metal foil made of the above-mentioned metal can be mentioned. The method of attaching, etc.

And, from the viewpoint of providing interlayer adhesion of other layers laminated with the non-thermally expandable base material layer (Y1-2), when the non-thermally expandable base material layer (Y1-2) contains a resin, The surface of the non-heat-expandable base material layer (Y1-2) can also be subjected to surface treatment and easy-adhesive treatment by oxidation or embossing in the same manner as the above-mentioned heat-expandable base material layer (Y1-1). Or primer treatment.

In addition, when the non-thermally expandable base material layer (Y1-2) contains a resin, it may be contained in the resin composition (y) together with the resin, and may contain the above-mentioned additive for base material.

The non-thermally expandable base material layer (Y1-2) is a non-thermally expandable layer judged by the above method. Therefore, as the volume change rate (%) of the non-thermally expandable base material layer (Y1-2) calculated by the above formula is less than 5%, preferably less than 2%, preferably less than 1%, More preferably, it is less than 0.1%, and more preferably, it is less than 0.01%.

In addition, in the non-thermally expandable base material layer (Y1-2), thermally expandable particles may be contained as long as the volume change rate is within the above-mentioned range. For example, by selecting the resin contained in the non-thermally expandable base material layer (Y1-2), even if thermally expandable particles are contained, the volume change rate can be adjusted to the above-mentioned range. However, the less the content of the thermally expandable particles in the non-thermally expandable base material layer (Y1-2), the better. Specifically, the content of heat-expandable particles is usually less than 3% by mass, preferably less than 1% by mass, and more preferably It is less than 0.1 mass %, more preferably less than 0.01 mass %, more preferably less than 0.001 mass %. It is preferable that the upper layer does not contain heat-expandable particles in the non-heat-expandable base material layer (Y1-2).

＜Adhesive layer (X1)＞ The adhesive layer (X1) included in the adhesive sheet (I) used in the first aspect of the present invention can be formed of an adhesive composition (x1) containing an adhesive resin. Furthermore, the adhesive composition (x1) may contain adhesive agent additives, such as a crosslinking agent, an adhesive agent, a polymeric compound, and a polymerization initiator, as needed. Each component contained in the adhesive composition (x1) will be described below. In addition, when the adhesive sheet (I) has the first adhesive layer (X11) and the second adhesive layer (X12), the first adhesive layer (X11) and the second adhesive layer (X12) may also contain Adhesive composition (x1) of each component shown below is formed.

(adhesive resin) As the adhesive resin used in one aspect of the present invention, the resin may have adhesiveness alone, and may be a polymer having a mass average molecular weight (Mw) of 10,000 or more. The mass average molecular weight (Mw) of the adhesive resin used in one aspect of the present invention is preferably from 10,000 to 2 million, more preferably from 20,000 to 1.5 million, from the viewpoint of improving the adhesive force. The best is 30,000 to 1 million.

Specific adhesive resins include rubber-based resins such as acrylic resins, urethane-based resins, and polyisobutylene-based resins, polyester-based resins, olefin-based resins, silicone-based resins, and polyvinyl ether resins. Department of resin, etc. These adhesive resins may be used alone or in combination of two or more. In addition, when these adhesive resins are copolymers having two or more structural units, the form of the copolymer is not particularly limited, and any of block copolymers, random copolymers, and graft copolymers may be used.

The adhesive resin used in one aspect of the present invention may be an energy ray-curable adhesive resin in which a polymerizable functional group is introduced into a side chain of the aforementioned adhesive resin. As this polymerizable functional group, a (meth)acryl group, a vinyl group, etc. are mentioned. Moreover, examples of energy rays include ultraviolet rays and electron rays, and ultraviolet rays are preferred.

In one aspect of the present invention, the adhesive resin preferably contains an acrylic resin from the viewpoint of exhibiting excellent adhesive force. And, when using the adhesive sheet (I) having the first adhesive layer (X11) and the second adhesive layer (X12), the first adhesive layer (X11) that is in contact with the resin film forming sheet (II) Containing acrylic resin in it can make it easy to form unevenness on the surface of the first adhesive layer.

The content ratio of the acrylic resin in the adhesive resin is 30 to 100% by mass relative to the total amount (100% by mass) of the adhesive resin contained in the adhesive composition (x1) or the adhesive layer (X1). % is more preferable, preferably 50-100 mass %, more preferably 70-100 mass %, still more preferably 85-100 mass %.

(acrylic resin) In one aspect of the present invention, as an acrylic resin used as an adhesive resin, for example, a polymer containing a constituent unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, A polymer containing a constituent unit derived from (meth)acrylate having a ring structure, etc.

The mass average molecular weight (Mw) of the acrylic resin is preferably from 100,000 to 1.5 million, more preferably from 200,000 to 1.3 million, more preferably from 350,000 to 1.2 million, still more preferably from 500,000 to 1.1 million.

The acrylic resin used in one aspect of the present invention has a constituent unit (a1) derived from an alkyl (meth)acrylate (a1') (hereinafter also referred to as "monomer (a1')") And an acrylic copolymer (A1) of a structural unit (a2) derived from a functional group-containing monomer (a2') (hereinafter also referred to as "monomer (a2')") is preferable.

The number of carbon atoms in the alkyl group of the monomer (a1') is preferably from 1 to 24, more preferably from 1 to 12, more preferably from 2 to 10, and still more preferably from the viewpoint of improvement of adhesive properties. 4 to 8. In addition, the alkyl group contained in the monomer (a1') may be a straight-chain alkyl group or a branched-chain alkyl group.

Examples of the monomer (a1') include meth (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2- Ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, etc. These monomers (a1') may be used alone or in combination of two or more. As the monomer (a1'), butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable.

The content of the structural unit (a1) is preferably 50 to 99.9 mass %, more preferably 60 to 99.0 mass %, more preferably 70 mass % with respect to all the structural units (100 mass %) of the acrylic copolymer (A1). ~97.0% by mass, more preferably 80-95.0% by mass.

Examples of the functional group contained in the monomer (a2') include hydroxyl group, carboxyl group, amino group, epoxy group and the like. In other words, examples of the monomer (a2') include hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, and the like. These monomers (a2') may be used alone or in combination of two or more. Among these, monomers (a2') are preferably hydroxyl-containing monomers and carboxyl-containing monomers.

As a hydroxyl group-containing monomer, the thing similar to the said hydroxyl group containing compound is mentioned, for example.

Examples of carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid; And its anhydrous, 2-(acryloxy)ethyl succinate, 2-carboxyethyl (meth)acrylate, etc.

The content of the structural unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, more preferably 1.0% to the total structural units (100% by mass) of the acrylic copolymer (A1). ~30% by mass, more preferably 3.0-25% by mass.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2'). And, for the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is 70 to 100% by mass relative to the total structural units (100% by mass) of the acrylic copolymer (A1). Preferably, it is 80-100 mass %, More preferably, it is 90-100 mass %, More preferably, it is 95-100 mass %.

Examples of the monomer (a3') include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; butadiene, isoprene, and chloroprene. and other diene monomers; cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, bicyclic Pentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylate with a ring structure such as imide (meth)acrylate; styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acrylmorpholine, N-ethylene Base pyrrolidone etc.

In addition, the acrylic copolymer (A1) can also be used as an energy-ray-curable acrylic copolymer in which a polymerizable functional group is introduced into the main chain and/or side chain. The polymerizable functional group and the energy ray are as described above. In addition, the polymerizable functional group can be introduced by reacting the above-mentioned acrylic copolymer having the constituent units (a1) and (a2) with the following polymerizable compound (Xa) having A substituent and a polymerizable functional group to which the functional group of the structural unit (a2) of the acrylic copolymer is bonded. Examples of the polymerizable compound (Xa) include (meth)acryloxyethyl isocyanate, methyl-isopropenyl-α,α-dimethylbenzyl isocyanate, (meth)acryl Isocyanate, allyl isocyanate, glycidyl (meth)acrylate, (meth)acrylic acid, etc.

(crosslinking agent) In one aspect of the present invention, when the adhesive composition (x1) contains an adhesive resin having a functional group, such as the above-mentioned acrylic copolymer (A1), it is preferable to further contain a crosslinking agent. The cross-linking agent reacts with an adhesive resin having a functional group, uses the functional group as a cross-linking origin, and cross-links the adhesive resins.

As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelating agent type crosslinking agent etc. are mentioned, for example. 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 from the viewpoints of improving cohesion and adhesion, and ease of availability.

Although the content of the crosslinking agent is appropriately adjusted by the number of functional groups in the adhesive resin, it is preferably 0.01 to 10 parts by mass for 100 parts by mass of the adhesive resin with functional groups, more preferably It is 0.03-7 mass parts, More preferably, it is 0.05-5 mass parts.

(adhesion imparting agent) In one aspect of the present invention, the adhesive composition (x1) may further contain an adhesive agent from the viewpoint of further improving the adhesive force. The so-called "adhesion-imparting agent" in this specification is a component that can assist in improving the adhesive force of the above-mentioned adhesive resin. Resin makes the difference. The mass average molecular weight (Mw) of the adhesion imparting agent is preferably 400-10000, more preferably 500-8000, more preferably 800-5000.

Examples of tackifiers include rosin-based resins, terpene-based resins, styrene-based resins, pentene produced by thermal decomposition of naphtha, isoprene, piperine, and 1,3-pentane C5-based petroleum resins obtained by copolymerizing C5 fractions such as dienes, indene produced by thermal decomposition of naphtha, C9-based petroleum resins obtained by copolymerizing C9 fractions such as vinyltoluene, and hydrogenation of these Hydrogenated resins, etc.

The softening point of the adhesion imparting agent is preferably from 60 to 170°C, more preferably from 65 to 160°C, more preferably from 70 to 150°C. In addition, in this specification, the "softening point" of an adhesive agent shows the value measured based on JISK2531. The tackifier may be used alone, or two or more kinds having different softening points or structures may be used in combination. And when using 2 or more types of plural tackiness imparting agents, it is preferable that the weighted average of the softening points of these plural tackiness imparting agents is in the said range.

The content of the tackifier is preferably 0.01 to 65% by mass relative to the total amount (100% by mass) of the active ingredients of the adhesive composition (x1) or the total mass (100% by mass) of the adhesive layer (X1) , preferably 0.05 to 55% by mass, more preferably 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, even more preferably 1.0 to 40% by mass.

(photopolymerization initiator) In one aspect of the present invention, when the adhesive composition (x1) contains an energy ray-curable adhesive resin as the adhesive resin, it is preferable to further contain a photopolymerization initiator. By using an adhesive composition containing an energy ray-curable adhesive resin and a photopolymerization initiator, the adhesive layer formed from the adhesive composition is stable even when irradiated with relatively low-energy energy rays. The hardening reaction can be fully carried out, and the adhesive force can be adjusted to the desired range. Moreover, as a photoinitiator used by one aspect of this invention, the thing similar to what was added to the said non-solvent type resin composition (y1) is mentioned.

The content of the photopolymerization initiator is preferably 0.01-10 parts by mass, more preferably 0.03-5 parts by mass, more preferably 0.05-2 parts by mass, based on 100 parts by mass of the energy ray-curable adhesive resin.

(additive for adhesive) In one aspect of the present invention, the adhesive composition (x1) may contain adhesive additives generally used in adhesives in addition to the above-mentioned additives within the range that does not impair the effect of the present invention. Examples of such additives for adhesives include antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators (catalysts), and ultraviolet absorbers. In addition, each of these additives for adhesives may be used independently, and may use 2 or more types together.

When these adhesive additives are contained, the content of each adhesive additive 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.

And, as shown in Fig. 3, when the adhesive laminate 2 is used in the adhesive sheet (I) of the above-mentioned second aspect, the first adhesive layer (X11) of the heat-expandable adhesive layer can further contain a heat-expandable adhesive layer. Particles of heat-expandable adhesive composition (x11) formed. The thermally expandable particles are as described above. The content of thermally expandable particles is 1 to 70% by mass for the total amount (100% by mass) of the active ingredients of the thermally expandable adhesive composition (x11) or the total mass (100% by mass) of the thermally expandable adhesive layer % is more preferable, more preferably 2-60 mass %, more preferably 3-50 mass %, still more preferably 5-40 mass %.

On the other hand, when the adhesive layer (X1) is a non-heat-expandable adhesive layer, the content of heat-expandable particles in the non-heat-expandable adhesive composition of the forming material of the non-heat-expandable adhesive layer is preferably as small as possible. As the content of heat-expandable particles, it is less than 1% by mass with respect to the total amount (100% by mass) of the active ingredients of the non-heat-expandable adhesive composition or the total mass (100% by mass) of the non-heat-expandable adhesive layer Preferably, it is less than 0.1% by mass, more preferably less than 0.01% by mass, more preferably less than 0.001% by mass. The further layer is preferably one that does not contain heat-expandable particles in the non-heat-expandable adhesive composition or non-heat-expandable adhesive layer.

And, when the adhesive laminates 1c and 1d shown in FIG. 2 use the adhesive sheet (I) having the first adhesive layer (X11) and the second adhesive layer (X12) of the non-thermally expandable adhesive layer, the At 23°C, the storage shear modulus G'(23) of the first adhesive layer (X11) of the non-thermally expandable adhesive layer is preferably 1.0×10 ⁸ Pa or less, more preferably 5.0×10 ⁷ Pa or less, More preferably, it is 1.0×10 ⁷ Pa or less. If the storage shear elastic modulus G'(23) of the first adhesive layer (X11) which is not a heat-expandable adhesive layer is 1.0×10 ⁸ Pa or less, the adhesive laminates 1c and 1d as shown in FIG. 2 are constituted, for example. When the heat-expandable particles in the thermally-expandable base material layer (Y1-1) that have been heat-treated for separation are expanded, the surface of the first adhesive layer (X11) that is in contact with the adhesive sheet (II) can be easily Form bumps. As a result, an adhesive laminate can be easily separated by weak force at the interface P of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II). Furthermore, at 23°C, the storage shear elastic modulus G'(23) of the first adhesive layer (X11) of the non-thermally expandable adhesive layer is preferably 1.0×10 ⁴ Pa or more, more preferably 5.0×10 ⁴ Pa or more, more preferably 1.0×10 ⁵ Pa or more.

In addition, in this specification, the storage shear elastic modulus G'(23) of an adhesive layer represents the value measured by the method described in an Example.

[Constitution of Adhesive Sheet (II)] The adhesive sheet (II) included in the adhesive laminate used in the production method of the present invention has a substrate (Y2) and an adhesive layer (X2), and the substrate (Y2) is directly laminated to the adhesive sheet (I) . And, from the point of view of improving the interlayer adhesion between the base material (Y2) and the adhesive layer (X2), on the side surface where the adhesive layer of the base material (Y2) is laminated, the above-mentioned Surface treatment such as oxidation or embossing, easy-adhesive treatment, or primer treatment. In addition, in the adhesive laminate used in one aspect of the present invention, from the viewpoint of suppressing the adhesion of the residue of the adhesive layer (X2) to the cutting and/or grinding objects, it is possible for semiconductors having bumps, for example Adhesive sheet (II) is an adhesive sheet from the point of view of excellent followability of objects to be processed with large surface irregularities such as wafers, and from the point of view of those that make the adhesive force of the adhesive layer (X2) excellent in stability over time. (II) It is preferable to have an intermediate layer (Z2) between a base material (Y2) and an adhesive layer (X2). Also, for example, the surface of the substrate (Y2) on the side of the adhesive layer (X2) may be subjected to antistatic treatment. When the intermediate layer (Z2) is present, the surface of the substrate (Y2) on the intermediate layer (Z2) side may also be subjected to antistatic treatment.

From the viewpoint of easy separation at the interface P of the adhesive sheet (I) at one time with a weak force, the substrate (Y2) is preferably a non-thermally expandable substrate. In addition, before and after the aforementioned heat treatment, the adhesive layer (X2) is also preferably a non-thermally expandable adhesive layer from the viewpoint of maintaining good adhesion with the adherend. In addition, the intermediate layer (Z2) is also preferably a non-thermally expandable layer. Therefore, the volume change rate (%) of the substrate (Y2), the adhesive layer (X2) and the intermediate layer (Z2) calculated by the above formula is independently less than 5%, but less than 2%. Better, more preferably less than 1%, more preferably less than 0.1%, more preferably less than 0.01%. And it is more preferable that the base material (Y2), the adhesive layer (X2), and the intermediate layer (Z2) do not contain heat-expandable particles. The base material (Y2), the adhesive layer (X2), and the intermediate layer (Z2) will be described below.

＜Substrate (Y2)＞ As a formation material of a base material (Y2), the thing similar to the formation material of the said non-thermal expansion base material layer (Y1-2) is mentioned. In addition, the substrate (Y2) is preferably one containing a resin, and it is preferable to form a resin layer containing a resin on at least the surface of the substrate (Y2) on the side where the adhesive sheet (I) is laminated, and the substrate ( Y2) is more preferably a resin film or a resin sheet. In addition, among the resin film or the resin sheet, the object to be processed in the step (4) is also ground from the viewpoint that when the object to be processed is ground to be extremely thin, the object to be processed can be held stably. Polyethylene film, polypropylene film, ethylene-vinyl acetate copolymer (EVA) film, polyethylene terephthalate film are preferred, and ethylene-vinyl acetate copolymer (EVA) film is more preferred. Furthermore, the above-mentioned resin film or resin sheet may contain known fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and the like. In addition, the resin film or the resin sheet may be transparent, or may be colored or metal vapor-deposited as necessary. In addition, the surface of the substrate (Y2) laminated on the side of the adhesive sheet (I) can also be peeled from the viewpoint of easy separation at the interface P with a weak force after heat treatment for separation.

In addition, from the viewpoint that the substrate (Y2) is easy to prevent positional deviation when the object to be processed is attached to the adhesive layer (X2), and when the object to be processed is attached, it is easy to prevent displacement of the adhesive layer (X2). From the viewpoint of excessive trapping, the storage modulus E'(23) at 23°C is preferably 1.0×10 ⁶ Pa or more.

In addition, the base material (Y2) may contain heat-expandable particles as long as the volume change rate is within the above-mentioned range, but from the above viewpoint, the lower the content of heat-expandable particles in the base material (Y2), the better. The content of the heat-expandable particles in the substrate (Y2) is generally less than 3% by mass, preferably less than 1% by mass with respect to the total mass (100% by mass) of the substrate (Y2). It is preferably less than 0.1 mass %, more preferably less than 0.01 mass %, still more preferably less than 0.001 mass %. It is further preferable that the substrate (Y2) does not contain heat-expandable particles.

The thickness of the substrate (Y2) is preferably 5 to 500 μm, more preferably 15 to 300 μm, more preferably 20 to 200 μm. When the thickness of the substrate (Y2) is 5 μm or more, it tends to be excellent in deformation resistance at high temperature (dimensional stability). On the other hand, if the thickness of the base material is 500 μm or less, when at least one of cutting and grinding is applied to the object to be processed attached to the adhesive sheet (II), the vibration of the adhesive sheet (II) due to vibration can be suppressed. deformation, so it is easy to improve processing accuracy such as film thickness accuracy.

＜Adhesive layer (X2)＞ The adhesive layer (X2) of the resin film forming sheet (II) can be formed using the above-mentioned adhesive composition (x1), and the preferred components or the preferred ranges of the contents of each component are also related to the adhesive composition. (x1) is the same.

Among them, in one aspect of the present invention, the adhesive resin in the adhesive layer (X2) is biologically formed from an adhesive composition containing an energy ray-curable adhesive resin that introduces a polymerizable functional group into a side chain. The layer is preferably formed of an adhesive composition containing an energy ray-curable acrylic polymer (B) (hereinafter also referred to as "acrylic polymer (B)" or "component (B)"). Layers are better. In the adhesive layer (X2) formed by this adhesive composition, although it has the excellent adhesive force which can fully hold the object to be processed before energy-ray irradiation, after energy-ray irradiation, adhesive force will fall. Therefore, a processed product can be easily separated from the adhesive sheet (II).

The content of component (B) in the adhesive composition is preferably at least 70% by mass, preferably at least 80% by mass, more preferably 90% by mass, based on the total amount (100% by mass) of the adhesive composition The above is preferably at most 99.9% by mass, more preferably at most 99.0% by mass, more preferably at most 98.0% by mass.

The thickness of the adhesive layer (X2) is preferably 1-100 μm from the viewpoint of good adhesion, such as semiconductor wafers with bumps, etc., and good followability to objects to be processed with large surface unevenness. Preferably it is 1-75 micrometers, More preferably, it is 1-50 micrometers.

In addition, when the adhesive composition of the material forming the adhesive layer (X2) contains an energy-ray-curable adhesive resin such as an energy-ray-curable acrylic polymer (B), it further contains a crosslinking agent or a photopolymerizable resin. The starter is preferred. As the cross-linking agent, the same ones added to the above-mentioned acrylic resins can be mentioned, and the range of the content is also as shown above, by increasing the gel fraction of the adhesive layer (X2), and suppressing it at the time of separating the processed product. From the viewpoint of generation of paste residue in the processed product, 0.1 to 20 parts by mass is preferable, more preferably 0.5 to 15 parts by mass, and more preferably 1.0 to 10 parts by mass for 100 parts by mass of the adhesive resin having a functional group. parts by mass. As a photoinitiator, the same thing added to the above-mentioned non-solvent type resin composition (y1) is mentioned, and the range of content is also the same as the above. Moreover, other additives other than these may be contained. Next, the energy ray-curable acrylic polymer (B) contained in the adhesive composition will be described.

(Component (B): energy ray curable acrylic polymer (B)) The energy ray-curable acrylic polymer (B) used in one aspect of the present invention introduces a polymerizable functional group into a side chain and/or main chain of a non-energy ray-curable acrylic polymer Acrylic copolymers. Non-energy ray-curable acrylic polymers include, for example, acrylic polymers having a constituent unit derived from an alkyl (meth)acrylate having a linear or branched chain, and acrylic polymers having Acrylic polymers, etc., which are the constituent units of (meth)acrylate. The polymerizable functional group is preferably a (meth)acryl group from the viewpoint of ease of introduction into a non-energy ray-curable acrylic polymer as described above.

(B) The mass average molecular weight (Mw) of the component is preferably 100,000 to 1.5 million, more preferably 200,000 to 1.2 million, more preferably 250,000 to 1 million, more preferably 300,000 to 900,000, even more preferably 350,000 to 800,000.

As component (B), it contains an alkyl (meth)acrylate having an alkyl group having 1 to 18 carbon atoms from the viewpoint of forming an adhesive sheet whose adhesive force is effectively reduced by irradiation of energy rays. Constituent unit (b1) of (b1') (hereinafter also referred to as "monomer (b1')") and monomer (b2') derived from an energy group (hereinafter also referred to as "monomer (b2')") The acrylic copolymer (B0) of the constituent unit (b2) and the energy ray-curable acrylic copolymer (B1) obtained by reacting with the polymerizable compound (Xb) are preferred, and the energy ray-curable acrylic copolymer (B1) is preferably Copolymer (B1) is preferred. Moreover, although the form of the copolymerization of acryl-type copolymer (B0), (B1) is not specifically limited, Block copolymer, random copolymer, and graft copolymer may be sufficient.

The content of the acrylic copolymer (B1) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount (100% by mass) of the component (B) contained in the adhesive composition. , more preferably 90 to 100% by mass, more preferably 100% by mass.

The number of carbon atoms in the alkyl group of the monomer (b1') is preferably 1-18, more preferably 1-12, more preferably 1-8, still more preferably 1-6. Examples of the monomer (b1') include those exemplified as the above-mentioned monomer (a1'), preferably butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate, and butyl (Meth)acrylates are preferred.

In the acrylic copolymer (B0), the content of the structural unit (b1) is equal to the total structural unit (100% by mass) of the acrylic copolymer (B0) from the viewpoint of improving the adhesive force of the formed adhesive layer. ) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, more preferably 70 to 98% by mass, even more preferably 80 to 96% by mass.

Examples of the monomer (b2') include those exemplified as the above-mentioned monomer (a2'), preferably at least one selected from the group consisting of hydroxyl group-containing monomers, carboxyl group-containing monomers, and epoxy group-containing monomers. The monomer is preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

In the acrylic copolymer (B0), the content of the structural unit (b2) is preferably 0.5 to 40 mass%, more preferably 1 ～30 mass %, more preferably 2～25 mass %, still more preferably 3～15 mass %. If the content of the structural unit (b2) is 0.5% by mass or more, the content of the structural unit (b2) having a functional group serving as a reaction point with the polymerizable compound (Xb) can be sufficiently ensured. , because the adhesive layer (X2) with high hardening property can be formed, when peeling off the cuttings and/or grinding objects from the adhesive layer (X2), it can prevent the adhesive layer ( The residue of X2) can be peeled off while it is generated. Moreover, when the content of the structural unit (b2) is 40% by mass or less, a sufficient pot life can be ensured when the adhesive layer (X2) is formed by applying a solution of the adhesive composition. In addition, the term "polymerizable compound (Xb)" means having a substituent capable of bonding to a functional group in the structural unit (b2) of the acrylic copolymer (B0) (hereinafter also referred to as "reactive functional group"), Compounds with polymerizable functional groups.

The acrylic copolymer (B0) may have a constituent unit (b3) derived from a monomer (b3') other than the above-mentioned monomers (b1') and (b2'). Examples of the other monomer (b3') include those exemplified as the above-mentioned monomer (a3').

In the acrylic copolymer (B0), the content of the structural unit (b3) is preferably 0 to 20% by mass, preferably 0, based on the total structural units (100% by mass) of the acrylic copolymer (B0). -10 mass %, More preferably, it is 0-5 mass %, More preferably, it is 0-1 mass %. In addition, the above-mentioned monomers (b1') to (b3') can be used alone or in combination of two or more.

The energy ray-curable acrylic copolymer (B1) is obtained by reacting the acrylic copolymer (B0) having the above-mentioned structural units (b1) and (b2) with the polymerizable compound (Xb). Examples of the polymerizable compound (Xb) include those exemplified as the above-mentioned polymerizable compound (Xa), but these have 1 to 5 polymerizable functional groups per molecule while having reactive functional groups. Compounds of these are preferred. Examples of the reactive substituent include isocyanate groups, carboxyl groups, epoxy groups, and the like, and isocyanate groups are preferred. As said polymerizable functional group, a (meth)acryl group, a vinyl group, etc. are mentioned as mentioned above, and a (meth)acryl group is preferable. As a specific polymerizable compound (Xb), (meth)acryloxyethyl isocyanate is preferable. And, a polymeric compound (Xb) can be used individually or in combination of 2 or more types.

Regarding the relationship between the number of functional groups of the acrylic copolymer (B0) and the compounding amount of the polymerizable compound (Xb) for the acrylic copolymer (B1), it can be obtained that although it has a moderate adhesive force before energy ray irradiation, it can be obtained after energy ray irradiation. From the point of view of an adhesive sheet whose adhesive force is effectively reduced after energy ray irradiation, the α value calculated by the following formula (1) is preferably 0.5-50, more preferably 1.0-40, more preferably 1.2-35, more preferably 1.5-30. Moreover, the said α value corresponds to the number of polymerizable functional groups which the acrylic copolymer (B1) has. Formula (1): α=[P _B ]×[Q _B ]×[R _B ]/100 (In formula (1), [P _B ] represents 100 parts by mass of all structural units of the acrylic copolymer (B0) [Q _B ] represents the equivalent of the polymerizable compound (Xb) with respect to 100 equivalents of the functional group derived from the functional group-containing monomer that the acrylic copolymer (B0) has.[ R _B ] represents the number of polymerizable functional groups possessed by the polymerizable compound (Xb).

＜Middle layer (Z2)＞ In one aspect of the present invention, the intermediate layer (Z2) is an intermediate layer-forming composition ( z2) formed. By providing the intermediate layer (Z2), an adhesive sheet (II) excellent in followability with respect to objects to be processed with rough surfaces such as semiconductor wafers and the like can be obtained. Therefore, when at least one of cutting and grinding is performed on the object to be processed to which the adhesive sheet (II) is attached, damage to the object to be processed can be suppressed, and cutting chips, grinding chips, cutting water, and grinding water, etc. can be prevented. Immersion into the attached surface of the object to be processed and the adhesive sheet (II). In addition, the intermediate layer (Z2) may or may not have adhesiveness.

The thickness of the intermediate layer (Z2) is the degree of unevenness of the object to be processed. For example, when the object to be processed is a semiconductor wafer or a semiconductor chip, the bump height of the semiconductor wafer or semiconductor chip can be appropriately selected, ranging from 10 to 800 μm More preferably, it is preferably 15-600 μm, more preferably 20-400 μm. When the thickness of the intermediate layer (Z2) is 10 μm or more, the followability to the object to be processed with a large difference in unevenness can be improved. On the other hand, when the thickness of the intermediate layer is 800 μm or less, deformation of the adhesive sheet (II) is easily suppressed.

The intermediate layer-forming layer composition (z2) of the material forming the intermediate layer (Z2) is used to improve the adhesion between the intermediate layer (Z2) and the adhesive layer (X2) of the adhesive sheet (II) after being irradiated with energy rays Or, when the cuttings and/or grindings are peeled from the adhesive sheet (II), the fracture of the adhesive layer (X2) or the residue of the adhesive layer (X2) on the surface of the cuttings and/or grindings From the viewpoint of suppressing generation, the non-energy ray-curable acrylic polymer (C) (hereinafter also referred to as "acrylic polymer (C)" or "component (C)") and a mass average molecular weight of 5 An energy ray-curable acrylic polymer (D) of 10,000 to 250,000 (hereinafter also referred to as "acrylic polymer (D)" or "component (D)") is preferable. Also, from the viewpoint of further improving the adhesion between the intermediate layer (Z2) and the adhesive layer (X2) after energy ray irradiation, the content of component (D) in the intermediate layer forming composition (z2) With respect to 100 parts by mass of the component (C), it is preferably at least 25 parts by mass, preferably at least 30 parts by mass, more preferably at least 37 parts by mass, still more preferably at least 40 parts by mass. Furthermore, in one aspect of the present invention, from the viewpoint of suppressing leaching from a part of the intermediate layer (Z2) at the edge of the adhesive sheet (II), (D) in the intermediate layer forming composition (z2) The content of the component is preferably at most 150 parts by mass, preferably at most 140 parts by mass, more preferably at most 130 parts by mass, with respect to 100 parts by mass of the component (C).

The total content of component (C) and component (D) in the intermediate layer forming composition (z2) is 70% by mass or more with respect to the entire amount (100% by mass) of the intermediate layer forming composition (z2) Preferably, it is at least 80% by mass, more preferably at least 90% by mass, more preferably at most 99.9% by mass, preferably at most 99.0% by mass, more preferably at most 98.0% by mass.

Moreover, it is preferable that the composition (z2) for intermediate|middle layer formation further contains a photoinitiator or a crosslinking agent in addition to said (C) component and (D) component. Moreover, other additives other than these may also be contained. Examples of the crosslinking agent include the same ones as those added to the above-mentioned acrylic resin, and the range of the content is also as described above. Examples of the photopolymerization initiator include the same ones as those added to the above-mentioned solvent-free resin composition (y1), and the range of the content is also the same as above. Moreover, other additives other than these may be contained. The non-energy ray-curable acrylic polymer (C) and the energy ray-curable acrylic polymer (D) contained in the intermediate layer forming composition (z2) will be described below.

(Component (C): Non-energy ray curable acrylic polymer (C)) Examples of non-energy ray-curable acrylic polymers (C) include polymers having a constituent unit derived from an alkyl (meth)acrylate having a linear or branched chain, and polymers having a constituent unit derived from an alkyl group having a ring. Polymers of constituent units of (meth)acrylates with a similar structure, etc.

(C) The mass average molecular weight (Mw) of the component is preferably 300,000 to 1.5 million, more preferably 350,000 to 1.3 million, more preferably 400,000 to 1.2 million, more preferably 400,000 to 1.1 million, more preferably The best is 450,000 to 900,000.

As component (C), from the viewpoint of compatibility with component (D), an alkyl (meth)acrylate (c1') (hereinafter also referred to as " acrylic acid having a constituent unit (c1) derived from a monomer (c1')") and a constituent unit (c2) derived from a functional group-containing monomer (c2') (hereinafter also referred to as "monomer (c2')") A copolymer (C1) is preferred, and an acrylic copolymer (C1) is preferred. Moreover, although the form of the copolymerization of an acryl-type copolymer (C1) is not specifically limited, Block copolymer, a random copolymer, and a graft copolymer may be sufficient.

The content of the acrylic copolymer (C1) is preferably 70 to 100% by mass, preferably It is 80-100 mass %, More preferably, it is 90-100 mass %, More preferably, it is 100 mass %.

The carbon number of the alkyl group contained in the monomer (c1') is preferably from 4 to 12, more preferably from 4 to 8, even more preferably from 4 to 8 from the viewpoint of compatibility with the component (D). 6.

Examples of the monomer (c1') include the same ones as those described above for the monomer (a1'). Among these, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are also preferable, and butyl (meth)acrylate is more preferable.

In the acrylic copolymer (C1), the content of the structural unit (c1) is preferably 50 to 99.5% by mass, more preferably 60% with respect to the total structural units (100% by mass) of the acrylic copolymer (C1). % to 99% by mass, more preferably 70 to 95% by mass, more preferably 80 to 93% by mass. When the content of the structural unit (c1) is 50% by mass or more, it is preferable because an adhesive sheet with good followability to an object to be processed with a large difference in unevenness is obtained. Moreover, when the content of a structural unit (c1) is 99.5 mass % or less, since the content of a structural unit (c2) can fully be ensured, and the compatibility with (D) component becomes favorable, it is preferable.

In addition, in the acrylic copolymer (C1), as the constituent unit (c1), there may be a compound derived from an alkane having a carbon number of 4 or more (preferably 4 to 12, preferably 4 to 8, more preferably 4 to 6). The constituent unit (c11) of the alkyl (meth)acrylate of the group is preferable. The content ratio of the structural unit (c11) in the structural unit (c1) is preferably 60% by mass or more with respect to the total amount (100% by mass) of the structural unit (c1) contained in the acrylic copolymer (C1), It is preferably at least 70% by mass, more preferably at least 80% by mass, still more preferably at least 85% by mass, and more preferably at most 100% by mass.

Examples of the functional group contained in the monomer (c2') include the same ones as those contained in the above-mentioned monomer (a2'). Concrete monomers (c2') include the same ones as those for the above-mentioned monomers (a2'). Among these, one or more selected from the group consisting of hydroxyl group-containing monomers, carboxyl group-containing monomers, and epoxy group-containing monomers is also preferable, and carboxyl group-containing monomers are more preferable. Specific examples of the hydroxyl group-containing monomer, carboxyl group-containing monomer, and epoxy group-containing monomer are the same as those for the above-mentioned monomer (a2').

In the acrylic copolymer (C1), the content of the structural unit (c2) is preferably 0.5 to 50% by mass, more preferably 1 ~40% by mass, more preferably 5-30% by mass, more preferably 7-20% by mass. When the content of the structural unit (c2) is 0.5% by mass or more, it is preferable because the compatibility with the (D) component can be improved. Moreover, when the content of the structural unit (c2) is 50% by mass or less, it is preferable because an adhesive sheet with good followability to an adhesive having a large difference in unevenness can be obtained.

The acrylic copolymer (C1) may have a structural unit (c3) derived from a monomer (c3') other than the above-mentioned monomers (c1') and (c2'). Examples of the other monomer (c3') include the same ones as those of the above-mentioned monomer (a3').

In the acrylic copolymer (C1), the content of the structural unit (c3) is preferably 0 to 30% by mass, preferably 0, based on the total structural units (100% by mass) of the acrylic copolymer (C1). -20 mass %, More preferably, it is 0-10 mass %, More preferably, it is 0-5 mass %. Furthermore, the above-mentioned monomers (c1') to (c3') can be used alone or in combination of two or more.

(Component (D): energy ray curable acrylic polymer (D)) The energy ray-curable acrylic polymer (D) is an acrylic polymer into which a polymerizable functional group is introduced for a non-energy ray-curable acrylic polymer. In addition, the above-mentioned polymerizable functional group is introduced into the main chain and/or side chain of a non-energy ray-curable acrylic polymer. Since the intermediate layer contains the component (D), it is considered that the component (D) reacts with the component (B) in the adhesive layer (X2) to bond when irradiated with energy rays, improving the adhesiveness of the intermediate layer of the sheet (II). (Z2) Adhesion with the adhesive layer (X2). Also, since the adhesive layer (X2) and the intermediate layer (Z2) are hardened, it is considered that sticky residue can be suppressed. Therefore, it is possible to suppress the residue of the adhesive layer (X2) at the time of peeling off the cut and/or ground matter from the adhesive sheet (II).

Examples of non-energy ray-curable acrylic polymers include acrylic polymers having a constituent unit derived from an alkyl (meth)acrylate having a linear or branched chain, or having a Acrylic polymers, etc., are structural units of (meth)acrylate.

The polymerizable functional group may be a group containing an energy ray polymerizable carbon-carbon double bond, for example, a (meth)acryl group, a vinyl group, etc., but from the viewpoint of being easy to introduce energy ray polymer , preferably (meth)acryl. In addition, the energy ray polymerizable group may be bonded to the main chain or side chain of the non-energy ray curable acrylic polymer via an alkylene group, an epoxy group, a polyoxyalkylene group, etc. .

(D) The mass average molecular weight (Mw) of the component is preferably 50,000 to 250,000, more preferably 60,000 to 220,000, more preferably 70,000 to 200,000, more preferably 80,000 to 180,000, and even more preferably The best is 85,000 to 150,000. If the Mw of the component (D) is less than 50,000, the temporal stability of the obtained adhesive sheet tends to deteriorate. In other words, when the adhesive sheet is stored for a long period of time, part of the component (D) moves into the adhesive layer, and the adhesive force of the adhesive sheet becomes unstable. After energy ray irradiation, the adhesive layer (X2) Easily overhardened. As a result, when the adhesive sheet is used after being stored for a long period of time, or when it is placed for a long period of time in a state where the object to be processed is attached, the adhesiveness between the intermediate layer (Z2) and the adhesive layer (X2) after energy ray irradiation It becomes insufficient, so when the adhesive sheet is peeled off, residues of the adhesive layer (X2) may adhere to breaks of the adhesive layer (X2) or cut and/or ground objects. On the other hand, when the Mw of the component (D) exceeds 250,000, the adhesion between the intermediate layer (Z2) and the adhesive layer (X2) after energy ray irradiation is likely to deteriorate, and the cutting and grinding objects will be separated from the adhesive. When the sheet (II) is peeled off, residues of the adhesive layer (X2) may adhere to breaks in the adhesive layer (X2) or to cut and/or ground objects.

Component (D) is an adhesive sheet with excellent stability over time, and an adhesive sheet with improved adhesion after energy ray irradiation of the formed intermediate layer (Z2) and adhesive layer (X2) From the point of view, it is better to contain an energy ray-curable acrylic copolymer (D1), which has energy ray-curable acrylic copolymer (D1) derived from an alkyl group having 1 to 18 carbon The constituent unit (d1) of the alkyl (meth)acrylate (d1') (hereinafter also referred to as "monomer (d1')") and the functional group-containing monomer (d2') (hereinafter also referred to as The acrylic copolymer (D0) of the constituent unit (d2) of "monomer (d2')") reacts with the polymerizable compound (Xd) and is curable by energy rays (D1 ) is preferred. Moreover, the form of the copolymerization of an acryl-type copolymer (D0), (D1) is not specifically limited, A block copolymer, a random copolymer, and a graft copolymer are all possible.

The content of the acrylic copolymer (D1) is preferably 70 to 100% by mass, more preferably 80-100 mass %, More preferably, it is 90-100 mass %, More preferably, it is 100 mass %.

The number of carbon atoms in the alkyl group of the monomer (d1') is preferably 4-12, more preferably 4-8, even more preferably 4-6. Examples of the monomer (d1') include those exemplified as the above-mentioned monomer (a1'). Among these, butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate is also preferable, and butyl (meth)acrylate is more preferable.

In the acrylic copolymer (D0), the content of the structural unit (d1) is preferably 50 to 99% by mass, more preferably 55% with respect to the total structural units (100% by mass) of the acrylic copolymer (D0). % to 95% by mass, more preferably 60 to 90% by mass, more preferably 65 to 85% by mass. When the content of the structural unit (d1) is 50% by mass or more, it is preferable because the shape of the formed intermediate layer (Z2) can be sufficiently maintained. In addition, if the content of the structural unit (d1) is 99% by mass or less, the content of the structural unit (d2) having a functional group serving as a reaction point with the polymerizable compound (Xd) can be sufficiently ensured, and the amount of the structural unit (d2) can be increased. The adhesion between the formed intermediate layer (Z2) and the adhesive layer (X2) after energy ray irradiation is better.

Examples of the monomer (d2') include those exemplified as the above-mentioned monomer (a2'), preferably at least one selected from the group consisting of hydroxyl-containing monomers, carboxyl-containing monomers, and epoxy-containing monomers. Hydroxyl monomer is preferred, hydroxyacrylic acid (meth)acrylate is more preferred, and 2-hydroxyethyl (meth)acrylate is preferred.

In the acrylic copolymer (D0), the content of the structural unit (d2) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass relative to the total structural units (100% by mass) of the acrylic copolymer (D0). % by mass, more preferably 10 to 40% by mass, more preferably 15 to 35% by mass. When the content of the constituent unit (d2) is 1% by mass or more, it is desired to improve the adhesion between the formed intermediate layer (Z2) and the adhesive layer (X2) after energy ray irradiation, so as to ensure sufficient adhesion with the polymerization. The reaction point of the active compound (Xd) is preferred. Moreover, when the content of a structural unit (d2) is 50 mass % or less, since the shape of the intermediate layer (Z2) formed can fully be maintained, it is preferable.

The acrylic copolymer (D0) may have a constituent unit (b3) derived from a monomer (d3') other than the above-mentioned monomers (d1') and (d2'). Examples of the other monomer (d3') include those exemplified as the above-mentioned monomer (a3').

In the acrylic copolymer (D0), the content of the structural unit (d3) is preferably 0 to 30% by mass, preferably 0, based on the total structural units (100% by mass) of the acrylic copolymer (D0). -20 mass %, More preferably, it is 0-10 mass %, More preferably, it is 0-5 mass %. In addition, the above-mentioned monomers (d1') to (d3') may be used alone or in combination of two or more.

The energy ray-curable acrylic copolymer (D1) is formed by reacting the functional group in the constituent unit (d2) of the acrylic copolymer (D0) with the polymerizable compound (Xd). The polymerizable functional group which it has is introduced into at least one of the main chain and the side chain of an acrylic-type copolymer (D0).

The polymerizable compound (Xd) is a compound having a polymerizable functional group, and is not particularly limited as long as it is a compound having a reactive functional group. Furthermore, among the polymerizable compounds (Xd), compounds having 1 to 5 polymerizable functional groups per molecule while having the above-mentioned reactive substituents are also preferable. Examples of the reactive substituent include isocyanate groups, carboxyl groups, epoxy groups, and the like, and isocyanate groups are preferred. As said polymerizable functional group, a (meth)acryl group, a vinyl group, etc. are mentioned as mentioned above, and a (meth)acryl group is preferable.

Specific examples of the polymerizable compound (Xd) include the same compounds as those for the above-mentioned polymerizable compound (Xb). A polymeric compound (Xd) can be used individually or in combination of 2 or more types. Among them, from the viewpoint of compounds having a preferred isocyanate group as the above-mentioned reactive substituent and having an appropriate distance between the acrylic copolymer (D0) and the energy ray polymerizable group, (meth)acryl Oxyethyl isocyanate is preferred.

Regarding the acrylic copolymer (D1), regarding the relationship between the number of functional groups possessed by the acrylic copolymer (D0) and the compounding amount of the polymerizable compound (Xd), the relationship between the formed intermediate layer (Z2) and the adhesive layer ( From the point of view of the adhesiveness after energy ray irradiation of X2), the β value calculated from the following formula (2) is preferably 1 to 50, more preferably 2 to 40, more preferably 3 to 35, more preferably More preferably, it is 5-30. In addition, the said β value corresponds to the energy ray polymeric base number which an acryl-type copolymer (D1) has. Formula (2): β=[P _d ]×[Q _d ]×[R _d ]/100 (In formula (2), [P _d ] represents 100 parts by mass of all structural units of the acrylic copolymer (D0) The content of the constituent unit (d2). [Q _d ] represents the equivalent of the polymerizable compound (Xd) to 100 equivalents of the functional group derived from the functional group-containing monomer possessed by the acrylic copolymer (D0). [ R _d ] represents the number of polymerizable functional groups possessed by the polymerizable compound (Xd).

(Other additives contained in the intermediate layer forming composition) Other additives may be contained in the intermediate layer forming composition (z2) within the range not impairing the effects of the present invention. Examples of other additives include antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, and tackifiers. When these additives are contained, the content of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.01 to 2 parts by mass, with respect to 100 parts by mass of the (A) component.

＜Releasable Material＞ In the adhesive laminate of one aspect of the present invention, a release material may be further laminated on the surfaces of the adhesive layers (X1) and (X2) attached to the object to be processed. As the release material, there may be mentioned a release sheet subjected to both-side release treatment, or a release sheet subjected to one-side release treatment, etc., and one in which a release agent is applied to a base material for the release material.

As the base material for the release material, for example, paper such as high-quality paper, cellophane, kraft paper; polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalene di Polyester resin films such as formate resins, plastic films such as olefin resin films such as polypropylene resins and polyethylene resins, etc.

Examples of release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resin etc.

The thickness of the peeling material is not particularly limited, but it is preferably 10-200 μm, more preferably 25-170 μm, more preferably 35-80 μm.

＜Physical properties of adhesive sheet (II)＞ In one aspect of the present invention, it is preferable that the adhesive sheet (II) satisfies 1 or more of the following requirements (α) to (γ) from the viewpoint of easier cutting and grinding in step (4), It is preferable to satisfy any two of the following requirements (α) to (γ), and it is more preferable to satisfy all of the requirements (α) to (γ). ・Requirement (α): The Young's modulus of the substrate (Y2) is 1.0 MPa or more; ・Requirement (β): The thickness of the substrate (Y2) is 5 μm or more; ・Requirement (γ): The storage modulus G' (23°C) of the adhesive layer (X2) is 0.10 MPa or more. Also, from the standpoint of easier cutting and grinding in step (4), the Young's modulus of the base material (Y2) specified in the requirement (α) is preferably 1.0 to 1000 MPa, and 1.5 to 800 MPa More preferably, 2.0-500MPa is more preferred. Also, from the standpoint of easier cutting and grinding in step (4), the thickness of the substrate (Y2) specified in the requirement (β) is preferably 5 to 250 μm, more preferably 10 to 230 μm , 20-210 μm is better. Also, from the standpoint of easier cutting and grinding in step (4), the storage modulus G' (23°C) of the adhesive layer (X2) specified in the requirement (γ) is preferably 0.10 to 1 MPa , preferably 0.12-0.9MPa, more preferably 0.14-0.8MPa.

[Each step of the manufacturing method of the processed product] Next, each step of the manufacturing method of the processed product of the present invention will be described in detail. The method for producing a processed product of the present invention is a method for producing a processed product subjected to at least one of cutting and grinding using an adhesive laminate, wherein the adhesive laminate comprises: a substrate (Y1) and an adhesive layer (X1), and a thermally expandable adhesive sheet (I) containing thermally expandable particles at a thermal expansion start temperature (t) in any layer, and an adhesive sheet (II) having a substrate (Y2) and an adhesive layer (X2) , and it is formed by direct lamination of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), The foregoing manufacturing method has the following steps (1) to (3) in sequence ・Step (1): The surface of the adhesive layer (X1) of the above-mentioned adhesive laminate is attached to the support body, and the step of attaching an additional object to the surface of the adhesive layer (X2) of the above-mentioned adhesive laminate ・Step (2): The step of applying one or more processes to the aforementioned object to be processed ・Step (3): By heating above the thermal expansion start temperature (t) of the thermally expandable particles, while maintaining the state where the object to be processed is attached to the surface of the adhesive layer (X2) of the adhesive laminate, A step of separating the aforementioned adhesive laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II); Furthermore, the following step (4) is provided, ・Step (4): A step of applying at least one of cutting and grinding to the surface of the object to be processed which is opposite to the surface to which the adhesive layer (X2) is attached; The aforementioned step (4) is implemented in at least one of the following (X) and (Y), (X): As one or more of the above-mentioned processings, it is implemented in the aforementioned step (2); (Y): implemented after the aforementioned step (3).

The above-mentioned adhesive laminate is used in the manufacturing method of this invention. Specifically, when the surface of the adhesive layer (X1) of the adhesive sheet (I) of the adhesive laminate is attached to the support, the surface of the adhesive layer (X2) of the adhesive sheet (II) of the adhesive laminate is Those who paste additional objects. Therefore, predetermined processing can be performed with the object to be processed fixed on the support. And after implementing the predetermined processing, the adhesive sheet (II) attached to the object to be processed can be easily separated from the adhesive sheet (I) at one time with weak force. In other words, the adhesive sheet (II) attached to the object to be processed can be easily separated from the support. Therefore, it is not necessary to attach the object to be processed to which the predetermined processing is applied to a new adhesive sheet, and it can be provided in the next step. Each step of the manufacturing method of the present invention will be described below with reference to FIG. 4 and FIG. 5 as appropriate.

＜Step (1)＞ Fig. 4(a) and Fig. 5(a) are cross-sectional schematic diagrams showing a state where an object to be attached is attached to a support body through an adhesive laminate. In step (1), as shown in Fig. 4(a) and Fig. 5(a), the additional objects 60, 70 are pasted on the support body 50 through the adhesive laminate 1a of the above-mentioned first aspect, and the aforementioned The support, the adhesive laminate, and the object to be processed are laminated in this order. 4 and 5, although the use of the adhesive laminate 1a shown in FIG. , the aforementioned adhesive laminate, and the aforementioned object to be processed are laminated in this order.

As shown in FIG. 4(a) and FIG. 5(a), in step (1), an additional object 60, 70 , attaching the adhesive layer (X1) of the adhesive sheet (I) included in the aforementioned adhesive laminate to the support body 50 .

Furthermore, examples of the object to be processed to be attached to the adhesive laminate include semiconductor wafers, semiconductor wafers, compound semiconductors, semiconductor packages, electronic components, sapphire substrates, displays, and panel substrates. In addition, the object to be processed may be a semiconductor wafer or the like on which dicing grooves are formed on the surface, and the surface side on which the dicing grooves are formed may be attached to the adhesive layer (X2) of the adhesive sheet (II). In addition, the object to be processed may be a semiconductor wafer or the like in which a modified region is previously formed by irradiation with laser light. In these cases, by performing grinding in step (4), the cutting groove or the modified region becomes the starting point of division, and the object to be processed can be divided. That is, when the object to be processed is a semiconductor wafer on which dicing grooves are formed on the surface, in the manufacturing method of one aspect of the present invention, the step (1) is the following step (1-C), and the aforementioned step (4) is Step (4-C) below. ・Step (1-C): attaching the surface of the adhesive layer (X1) of the aforementioned adhesive laminate to a support, and simultaneously attaching the aforementioned semiconductor crystal to the surface of the adhesive layer (X2) of the aforementioned adhesive laminate Procedure for a circle with faces cut into grooves ・Step (4-C): A step of grinding the surface of the aforementioned semiconductor wafer opposite to the sticking surface of the adhesive layer (X2) Also, when the object to be processed is a semiconductor wafer having a modified region serving as a starting point for division, in the manufacturing method according to an aspect of the present invention, step (4) is the following step (4-A). ・Step (4-A): A step of grinding the surface of the aforementioned semiconductor wafer opposite to the surface to which the adhesive layer (X2) is attached

The above-mentioned support body fixes the object to be processed in step (2), and is used to improve the precision of processing. It is preferable to stick the aforementioned support to the adhesive surface of the adhesive layer (X1) of the adhesive laminate. Therefore, the support body is preferably plate-shaped. Also, as shown in Figures 4 and 5, the surface area of the support 50 on the side attached to the adhesive surface 122a of the adhesive layer (X1) is preferably greater than the area of the adhesive surface 122a of the adhesive layer (X1). .

The material constituting the support is appropriately selected in consideration of the required properties such as mechanical strength and heat resistance according to the type of object to be processed or the processing performed in step (2). As the material constituting a specific 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 design plastic, super engineering design plastic, Resin materials such as polyimide resin and polyamide imide resin; composite materials such as glass epoxy resin, etc. Among them, SUS, glass and silicon wafers are also preferred. In addition, examples of engineering plastics include nylon, polycarbonate (PC), polyethylene terephthalate (PET), and the like. Examples of super-engineering plastics include polyphenylene sulfide (PPS), polyether sulfide (PES), and polyether ether ketone (PEEK).

The thickness of the support can be appropriately selected in consideration of required properties, etc., and is preferably 20 μm to 50 mm, more preferably 60 μm to 20 mm.

As temperature conditions in the step (1), it is sufficient that the expansion start temperature (t) of the heat-expandable particles is not reached.

＜Step (2)＞ In step (2), one or more processes are given to the aforementioned object to be processed attached to the adhesive layer (X2) of the adhesive laminate of the present invention in step (1). Examples of the processing to be performed in step (2) include encapsulation using resin on the object to be processed, processing to form a modified region on the object to be a starting point for division, circuit formation processing, etching, plating, etc. Coating treatment, sputtering treatment, vapor deposition treatment, protective film formation treatment, lamination treatment using a separately prepared adhesive sheet, etc. Also, the processing given in the step (2) may be at least one of cutting and grinding of the object to be processed. That is, the processing given in step (2) may include at least one of the steps of cutting the object to be processed and the step of grinding the object, or may not include the step of cutting the object to be processed and the step of grinding the object. of processing. The temperature condition in the step (2) is the same as that of the step (1), as long as it does not reach the expansion start temperature (t) of the heat-expandable particles. Hereinafter, as step (2), in the case of performing a process of forming a modified region to be a division starting point on the object to be processed (step (2-A)), the encapsulation process is performed using a resin for the object to be processed (step (2-A) The case of B)) is illustrated as an example.

(step (2-A)) The step (2-A) is a step in which the object to be processed is a semiconductor wafer, and a modified region to be a division starting point is formed on the semiconductor wafer. Specifically, as shown in FIG. 4(b), the surface of the semiconductor wafer and the side opposite to the sticking surface of the adhesive sheet (II) is used as the laser light incident surface, and the light-collecting point of the laser light becomes Inside the semiconductor wafer, a region 71 modified by multiphoton absorption or the like is formed. The modified region 71 functions as a starting point for dividing the semiconductor wafer by performing the grinding in step (4). And, in the manufacturing example shown in Fig. 4, although step (4) is implemented after step (3), after step (2-A), one of the processing as one or more of the steps (2) can be implemented The grinding of step (4). At this time, the individualized semiconductor wafer does not need to be separated from the adhesive sheet (II), and the individualized semiconductor wafer can be directly provided to the next step in a state attached to the adhesive sheet (II). That is, in the manufacturing method of one aspect of the present invention, the object to be processed is a semiconductor wafer, and one or more of the processing in step (2) includes the following step (2-A), ・Step (2-A): A step of forming a modified region to be a starting point of division on the aforementioned semiconductor wafer Step (4) is the following step (4-A), ・Step (4-A): A step of grinding the surface of the aforementioned semiconductor wafer opposite to the surface to which the adhesive layer (X2) is attached Step (4-A) is carried out in the following (X-A) or (Y-A), (X-A): As one or more of the above-mentioned processes, it is implemented after the above-mentioned step (2-A); (Y-A): implemented after the aforementioned step (3).

(step (2-B)) In the step (2-B), the object to be processed is a semiconductor wafer, and the peripheral portion of the aforementioned semiconductor wafer on the adhesive surface of the semiconductor wafer and the adhesive layer (X2) is covered with an encapsulation material, and the encapsulation material is hardened, A step of obtaining a hardened package formed by encapsulating the semiconductor wafer with a hardened packaging material.

As shown in FIG. 5 , when the manufacturing method of the present invention has step (2-B), in step (1), a semiconductor wafer 60 is used as the object to be processed. The semiconductor chip 60 can use conventionally known methods to form an integrated circuit composed of transistors, resistors, condensers and other circuit elements on the circuit surface. Preferably, the circuit surface of the semiconductor wafer 60 is placed so as to be covered with the adhesive surface of the adhesive layer (X2) of the adhesive sheet (II). For mounting of the semiconductor wafer, known devices such as a flip chip mounter and a mounter can be used. The arrangement layout and arrangement number of the semiconductor wafer 60 may be appropriately determined in accordance with the intended packaging form and production quantity.

Among them, as a manufacturing method of one aspect of the present invention, such as FOWLP, FOPLP, etc., the semiconductor wafer 60 is covered with an encapsulation material in an area larger than the wafer size, not only for the circuit surface of the semiconductor wafer 60, but also for the encapsulation material. It is preferable that the surface area is suitable for the package forming the redistribution layer. Therefore, the semiconductor wafer 60 is placed on a part of the adhesive surface of the adhesive layer (X2), and a plurality of semiconductor wafers 60 are preferably placed on the adhesive surface in a state of being arranged with a certain interval. It is preferable that the semiconductor wafers 60 are placed on the adhesive surface in a state of being arranged in a matrix of a plurality of rows and a plurality of columns at certain intervals. The interval between the semiconductor chips 60 may be appropriately determined in accordance with the intended package form and the like.

In step (2-B), the adhesive surface of the aforementioned semiconductor wafer 60 and at least the adhesive layer (X1) of the peripheral portion of the semiconductor wafer 60 is coated with a packaging material (hereinafter also referred to as "coating step"), This encapsulating material is cured to obtain a cured package 61 in which the aforementioned semiconductor chip 60 is encapsulated in the cured encapsulating material (hereinafter also referred to as "curing step"). The semiconductor chip 60 is mounted on a part of the adhesive surface of the adhesive layer (X2), forming the peripheral portion of the semiconductor chip 60 in the adhesive surface of the adhesive layer (X2). In other words, the peripheral portion of the semiconductor wafer 60 refers to the adhesive surface of the adhesive layer ( X2 ) corresponding to the gap between adjacent semiconductor wafers 60 among the plurality of semiconductor wafers 60 .

For the coating step of step (2-B), firstly, the peripheral portion of the semiconductor wafer 60 is coated with an encapsulation material on the adhesive surface between the semiconductor wafer 60 and the adhesive layer ( X2 ). The encapsulating material covers the entire exposed surface of the semiconductor chip CP, and also fills the gaps between the plurality of semiconductor chips CP.

The packaging material has a function of protecting the semiconductor chip CP and elements related thereto from the external environment. As the encapsulating material, any one can be appropriately selected from those used as semiconductor encapsulating materials, for example, an encapsulating material containing a thermosetting resin, or an encapsulating material containing an energy ray curable resin, etc. can be used. Also, even if the sealing material is solid at room temperature, such as granular or flake, it may be liquid in the form of a composition, but the thin-sheet sealing material is preferable from the viewpoint of workability.

Using a packaging material, as a method of covering the semiconductor wafer 60 and its peripheral portion, a method suitable for the semiconductor packaging process in the past is used, which is appropriately selected according to the type of packaging material, such as spin lamination method and vacuum pressure method. , vacuum lamination, spin coating, die coating, transfer molding, compression molding, etc.

And after performing the covering step, the encapsulating material is cured to obtain a cured package body 61 in which the semiconductor chip 60 is encapsulated by the cured encapsulating material. Furthermore, it is preferable to carry out the coating step and the hardening step of the step (2-B) at a temperature lower than the expansion start temperature (t) of the heat-expandable particles. Also, the covering step and the curing step can be performed separately, but in the covering step, when the sealing material is heated, the heating directly hardens the sealing material, and the covering step and the curing step can be performed simultaneously. And, in the production example shown in Figure 5, although step (4) is implemented after step (3), after step (2-B), as one of more than one processing in step (2), you can Implement as step (4). At this time, it is not necessary to separate the cured package from the adhesive sheet (II), and the cured package can be provided in the next step in a state attached to the adhesive sheet (II). That is, in the manufacturing method of one aspect of the present invention, the object to be processed is a semiconductor wafer, and one or more processes in step (2) include the following step (2-B), ・Step (2-B): Covering the peripheral portion of the aforementioned semiconductor chip and the aforementioned semiconductor chip on the adhesive surface of the adhesive layer (X2) with an encapsulation material, and hardening the encapsulation material to obtain the aforementioned semiconductor chip packaged in Steps of hardening the encapsulation material to form the hardened package Step (4) can be implemented in any of the following (X-B) and (Y-B). (X-B): As one or more of the aforementioned processes, it is implemented after the aforementioned step (2-B) (Y-B): implemented after the aforementioned step (3)

＜Step (3)＞ In step (3), by heat treatment at a temperature higher than the expansion start temperature (t) (heat treatment for separation), the adhesive sheet (I) and the base material of the adhesive sheet (II) of the adhesive laminate ( The interface P of Y2) is separated. 4( c ) and FIG. 5( c ) are cross-sectional schematic diagrams showing a state where separation occurs at the interface P by heat treatment for separation. Fig. 4(c) and Fig. 5(c) show the state in which the object to be processed, which is subjected to predetermined processing, is laminated on the adhesive sheet (II) and separated by heat treatment for separation.

The "temperature above the expansion start temperature (t)" in the heat treatment for separation in step (3) is above "expansion start temperature (t) + 10°C" and "expansion start temperature (t) + 60°C" The one is more preferable, and the one above "expansion start temperature (t) + 15°C" and "expansion start temperature (t) + 40°C" is more preferred.

In the state where the object to be processed is laminated (attached) in step (2), since the adhesive sheet (II) can be separated from the adhesive sheet (I) and separated from the support, it can be omitted. The operation of attaching the separated object to be processed to the adhesive sheet is provided in the next step.

＜Step (4)＞ In step (4), at least one of cutting and grinding is applied to the surface opposite to the sticking surface of the adhesive layer (X2) of the object to be processed. For example, by performing cutting on the object to be processed, the object to be processed can be divided into desired sizes. Also, by performing grinding, the object to be processed can be adjusted to a desired thickness. In addition, both cutting and grinding can be performed, and the division and thickness adjustment of the processed object can be performed.

Also, for example, as shown in FIG. 4( d ), the surface of the semiconductor wafer formed by irradiating the modified region as the starting point of division with laser light is ground on the side opposite to the surface to which the adhesive sheet (II) is attached, After making the semiconductor wafer into a thin and easy-to-cut state, by using the modified region 71 as the starting point of division to generate gaps 72 by using processing pressure such as grinding stones, the semiconductor wafer can be divided into individual pieces into a predetermined size and made into a semiconductor wafer. .

Moreover, as shown in FIG. 5( d ), by cutting the hardened package 61, the individual hardened package pieces 61a can be obtained after cutting the hardened package 61 into semiconductor wafer CP units. The method of cutting the cured package 61 into individual pieces is not particularly limited, and examples thereof include cutting means such as a dicing saw. Also, although not shown in the figure, the cured package 61 may be ground for the purpose of exposing the circuit surface of the semiconductor chip.

And, between steps (1) to (4), before step (1), and after step (4), other steps may be further included. For example, a rewiring forming step and the like may be included.

In addition, step (4) may be implemented as one of more than one processing in step (2) as described above, or may be implemented after step (3). Moreover, step (4) may be implemented after step (3) while being implemented as one of one or more processes in step (2). For example, as one of the one or more processes in step (2), grinding is performed on the surface opposite to the sticking surface of the adhesive layer (X2) of the object to be processed, and cutting may be performed after step (3). Also, as one of the one or more processes in step (2), only one direction of the surface opposite to the sticking surface of the adhesive layer (X2) of the object to be processed (for example, in the XY plane of the object to be processed) Cutting in the X-axis direction) to divide the object into booklets, and after step (3), only cut in another direction (such as the Y-axis direction in the XY plane of the object to be processed), or divide it into The booklet-shaped processing object is then shredded (for example, cut into a square shape) and divided. [Example]

The present invention will be described in more detail by the following examples, but the present invention is not limited to the following examples. In addition, the physical property values in the following manufacture examples and examples are values measured by the following methods.

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

＜Thickness measurement of each layer＞ The measurement was performed using a constant pressure thickness measuring device manufactured by TECLOCK CO., LTD. (Model: "PG-02J", standard specifications: JIS K6783, Z1702, Z1709).

<Average particle diameter (D ₅₀ ) of heat-expandable particles, 90% particle diameter (D ₉₀ )> Use a laser diffraction particle size distribution analyzer (for example, the product name "Mastersizer 3000" manufactured by Malvern Co., Ltd.) to measure the particle size at 23°C. Particle distribution of heat-expandable particles before expansion. And the cumulative volume frequency calculated from the smaller particle size of the particle distribution is equivalent to 50% and 90% of the particle size, respectively as "average particle size of thermally expandable particles (D ₅₀ )" and "90% of thermally expandable particles Particle diameter (D ₉₀ )”.

<Storage modulus E' of thermally expandable base material layer (Y1-1)> The formed heat-expandable base material layer (Y1-1) was made into the dimension of 5 mm in length x 30 mm in width x 200 micrometers in thickness, and what removed the peeling material was made into the test sample. Use a dynamic viscoelasticity measuring device (product name "DMAQ800" manufactured by TA Instruments Co., Ltd.), 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. Storage modulus E' of the test specimen at the specified temperature.

<Storage shear modulus G' of the first adhesive layer (X11), second adhesive layer (X12) and adhesive layer (X2)> Cut the formed 1st adhesive layer (X11), 2nd adhesive layer (X12) and adhesive layer (X2) into a circle with a diameter of 8 mm, remove the peeling material and stack them to make a test with a thickness of 3 mm sample. Using a viscoelasticity measurement device (use the device name "MCR300" manufactured by Anton Paar Company), under the conditions of the test start temperature 0 ° C, the test end temperature 300 ° C, the heating rate 3 ° C / min, the vibration frequency 1 Hz, by torsional shear The breaking method is to measure the storage shear elastic modulus G' of the test sample at a given temperature.

<Probe Viscosity 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 was used as a test sample. In an environment of 23°C and 50%RH (relative humidity), use a viscosity tester (product name "NTS-4800" manufactured by Nippon Special Sekki Co., Ltd.) to test the stickiness of the probe on the surface of the sample. The value is measured in accordance with JIS Z0237:1991. Specifically, after contacting a stainless steel detector with a diameter of 5mm on the surface of the test sample with a contact load of 0.98N/ ^cm2 for 1 second, the detector is measured at a speed of 10mm/second. The necessary force to detach from the surface of the sample, and use the obtained value as the probe viscosity value of the test sample.

<Measurement of Adhesive Strength of Adhesive Layer Before Heat Treatment for Separation> On the adhesive surface of the adhesive layer formed on the release film, a PET film (product name "Cosmo Shine A4100" manufactured by Toyobo Co., Ltd.) with a thickness of 50 μm was laminated to form an adhesive sheet for attaching the substrate. And remove the peeling film, attach the exposed adhesive surface of the adhesive layer to the stainless steel plate (SUS304 No. 360 grinding) of the adherend, and let it stand for 24 hours in an environment of 23°C and 50%RH (relative humidity). , under the same environment, according to JIS Z0237: 2000, by 180 ° tensile peeling method, at a tensile speed of 300mm/min, the adhesive force at 23°C was measured.

In the following examples, the details of the adhesive resin, additives, heat-expandable particles, and release material used to form each layer are as follows.

＜Adhesive resin＞ ・Acrylic copolymer (i): has a constituent unit derived from a raw material monomer composed of 2-ethylhexyl acrylate (2EHA)/2-hydroxyethyl acrylate (HEA)=80.0/20.0 (mass ratio) Acrylic copolymer of Mw600,000. ・Acrylic copolymer (ii): has a composition derived from 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 with a Mw of 600,000 as a constituent unit of the raw material monomer.

＜Additives＞ ・Isocyanate crosslinking agent (i): product name "Coronate L" manufactured by Tosoh Co., Ltd., solid content concentration: 75% by mass. - Photopolymerization initiator (i): product name "IRGACURE 184" manufactured by BASF Corporation, 1-hydroxy-cyclohexyl-phenyl-ketone.

<Heat-expandable particles> ・Heat-expandable particles (i): product name "Expancel 031DU40" of Japan Philite Co., Ltd., expansion start temperature (t) = 90°C, average particle diameter (D ₅₀ ) = 22μm, 90% particle diameter (D ₉₀ )=30 μm.

＜Releasable Material＞ ・Heavy release film: The product name "SP-PET382150" manufactured by Lintec Co., Ltd. has a polysiloxane-based release agent on one side of a polyethylene terephthalate (PET) film. For the release agent layer, thickness: 38 μm. ・Light release film: Lintec Co., Ltd. product name "SP-PET381031", which has a release agent layer formed of a silicone release agent on one side of the PET film, thickness: 38 μm.

[Example 1] For the adhesive laminate 1d shown in Figure 2(b), on the second adhesive layer (X12) of the adhesive sheet (I) and the adhesive layer (X2) of the adhesive sheet (II), there are further laminated release materials. For the constitution, an adhesive laminate with an intermediate layer (Z2) provided between the base material (Y2) and the adhesive layer (X2) of the adhesive sheet (II) was produced by the following procedure.

[1] Production of adhesive sheet (I) (1-1) 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (i) formed in the adhesive resin of the first adhesive layer (X11), add the above-mentioned isocyanate 5.0 parts by mass (solid content ratio) of the joint agent (i) was diluted with toluene and uniformly stirred to prepare an adhesive composition having a solid content concentration (active component concentration) of 25 mass%. And apply the adhesive composition on the surface of the release agent layer of the above-mentioned heavy-release film to form a coating film, and dry the coating film at 100°C for 60 seconds to form the first non-thermally expandable adhesive layer with a thickness of 5 μm. Adhesive layer (X11). Furthermore, the storage shear modulus G'(23) of the first adhesive layer (X11) at 23°C was 2.5×10 ⁵ Pa. Moreover, the adhesive force of the 1st adhesive layer (X11) measured by the said method was 0.3 N/25mm.

(1-2) In the second adhesive layer (X12), 0.8 parts by mass of the above-mentioned isocyanate-based crosslinking agent (i) (solid Component ratio) was diluted with toluene and uniformly stirred to prepare an adhesive composition with a solid content concentration (active component concentration) of 25% by mass. And apply the adhesive composition on the surface of the release agent layer of the 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 (X12) with a thickness of 10 μm. In addition, the storage shear modulus G'(23) of the second adhesive layer (X12) at 23°C was 9.0×10 ⁴ Pa. Moreover, the adhesive force of the 2nd adhesive layer (X12) measured by the said method was 1.0 N/25mm.

(1-3) Fabrication of base material (Y1) (1-3-1) Preparation of composition (y1-1) The terminal isocyanate urethane prepolymer obtained by reacting ester diol with isophorone diisocyanate (IPDI) is reacted with 2-hydroxyethyl acrylate to obtain a mass average molecular weight (Mw) of 5000 A 2-functional urethane acrylate oligomer. In addition, 40% by mass (solid content ratio) of isobornyl acrylate (IBXA) was added as an energy ray polymerizable monomer to 40% by mass (solid content ratio) of the urethane acrylate oligomer synthesized above. Component ratio) and 20% by mass (solid content ratio) of phenylhydroxypropyl acrylate (HPPA), based on the total amount (100 parts by mass) of the urethane acrylate oligomer and the energy ray polymerizable monomer Furthermore, 2.0 parts by mass (solid content ratio) of a photopolymerization initiator (i) and 0.2 parts by mass (solid content ratio) of a phthalocyanine pigment as an additive were added to prepare an energy ray-curable composition. And the above-mentioned heat-expandable particle (i) was added to this energy ray curable composition, and the non-solvent type composition (y1-1) which does not contain a solvent was prepared. Furthermore, the content of the thermally expandable particles (i) was 20% by mass with respect to the entire amount (100% by mass) of the composition (y1-1).

(1-3-2) The base material (Y1) is a non-thermally expandable base material made of polyethylene terephthalate (PET) film (product name "Cosmo Shine A4300" manufactured by Toyobo Co., Ltd.) with a thickness of 50 μm. ", probe viscosity value: 0mN/5mmφ), the prepared composition (y1-1) was coated on the surface to form a coating film. Furthermore, an ultraviolet irradiation device (product name "ECS-401GX" manufactured by Eye Graphics Co., Ltd.) and a high-pressure mercury lamp (product name "H04-L41" manufactured by Eye Graphics Co., Ltd.) were used at an illuminance of 160 mW/cm ² and a light intensity of 500 mJ/cm ² The coating film was cured by irradiating ultraviolet rays under certain conditions to form a thermally expandable substrate (Y-1) with a thickness of 50 μm. In addition, the said illuminance and light quantity at the time of ultraviolet irradiation are the values measured using the illuminance-light quantity meter (product name "UV Power Puck II" by EIT company). Moreover, the PET film of the said non-thermally expandable base material corresponds to a non-thermally expandable base material layer (Y1-2). And, as a sample for measuring the physical property value of the heat-expandable base material layer (Y1-1), the resin composition was coated on the surface of the release agent layer of the above-mentioned light release film to form a coating film, and the coating film was heated at 100°C. Drying was carried out for 120 seconds, and a heat-expandable substrate layer (Y1-1) with a thickness of 50 μm was also formed. And, according to the above-mentioned measurement method, the storage modulus and the probe viscosity value at each temperature of the thermally expandable base material layer (Y1-1) were measured. The measurement results are shown below.・Storage modulus E'(23) at 23℃＝5.0×10 ⁸ Pa ・Storage modulus E'(100) at 100℃＝4.0×10 ⁶ Pa ・Storage modulus E'(208 at 208℃ )＝4.0×10 ⁵ Pa ・Probe viscosity＝2mN/5mmφ

(1-4) Lamination of each layer Attach the non-heat-expandable base material layer (Y1-2) of the base material (Y1) prepared in the above (1-3) to the second adhesive layer (X12) formed in the above (1-2) , while attaching the thermally expandable base material layer (Y1-1) to the second adhesive layer (X12) formed in (1-2) above. And with light release film/second adhesive layer (X12)/non-thermally expandable substrate layer (Y1-2)/thermally expandable substrate layer (Y1-1)/first adhesive layer (X11)/heavy release film The adhesive sheet (I) is produced after lamination in the order described above.

[2] Production of adhesive sheet (II) (2-1) Formation of adhesive layer (X2) Add 8 parts by mass (solid content ratio) of the above-mentioned isocyanate-based crosslinking agent (i) to 100 parts by mass of the solid content of the above-mentioned acrylic copolymer (ii) of the adhesive resin, dilute with toluene, and stir uniformly to prepare An adhesive composition with a solid content concentration (active component concentration) of 25% by mass. And on the surface of the release agent layer of the above-mentioned heavy release film, apply the adhesive composition to form a coating film, and dry the coating film at 100°C for 60 seconds to form an adhesive layer (X2) with a thickness of 20 μm. Moreover, the adhesive force of the adhesive layer (X2) measured by the said method was 0.5 N/25mm.

(2-2) Substrate (Y2) The substrate (Y2) was a polyethylene terephthalate (PET) film (product name "Cosmo Shine A4300" manufactured by Toyobo Co., Ltd., probe viscosity: 0 mN/5 mmφ) with a thickness of 50 μm.

(2-3) Middle layer (Z2) (1) Preparation of composition for intermediate layer formation Add 100 parts by mass of non-energy ray-curable acrylic copolymer C1, 68 parts by mass of energy ray-curable acrylic copolymer D1, and 2.8 parts by mass of toluene diisocyanate crosslinking agent (trade name: BHS 8515, manufactured by Toyochem Corporation) part and 2.7 parts by mass of the photopolymerization initiator (i) above were diluted with ethyl acetate to prepare a solution of a composition for forming an intermediate layer having a solid content concentration (active ingredient concentration) of 35 mass%.

(2) Preparation of non-energy ray-curable acrylic copolymer C1 Add 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AAc) to ethyl acetate solvent, add 1.0 parts by mass of azobisisobutyronitrile (AIBN) as a polymerization initiator, and perform solution polymerization A non-energy ray-curable acrylic copolymer C1 (Mw: 500,000) was obtained.

(3) Preparation of energy ray curable acrylic copolymer D1 Add 62 parts by mass of butyl acrylate (BA), 10 parts by mass of methyl methacrylate (MMA) and 28 parts by mass of 2-hydroxyethyl acrylate (HEA) to ethyl acetate solvent as a polymerization initiation agent, 1.0 parts by mass of azobisisobutyronitrile (AIBN) was added to carry out solution polymerization, and after a certain period of time, an acrylic copolymer (BA/MMA/HEA=62/10/28 (mass %)) was obtained. Continuing with this acrylic copolymer, add methacryloxyethyl isocyanate in an amount of 80 equivalents of isocyanate groups with respect to 100 equivalents of total hydroxyl groups in the added HEA, and react to obtain Polymerized energy ray curable acrylic copolymer D1 (Mw: 100,000). The β value calculated from the above formula (2) in the energy ray-curable acrylic copolymer D1 was 22.4.

(4) Fabrication of the middle layer (Z2) On the peeled surface of the peeled sheet (trade name "SP-PET381031" manufactured by Lintec Co., Ltd., polysiloxane peeled polyethylene terephthalate film, thickness: 38 μm), the The prepared solution of the intermediate layer forming composition was applied to a thickness of 45 μm after drying to form a coating film. Next, after drying this coating film at 100 degreeC for 2 minutes, the intermediate layer (Z2) was formed, and the peeling sheet with an intermediate layer was produced. And, for this peeling sheet with an intermediate layer, two identical ones were produced, and the intermediate layers of the two peeling sheets with an intermediate layer were attached to each other to obtain an intermediate layer (Z2) with a thickness of 90 μm. Laminate board held hostage.

(2-4) Lamination of each layer The intermediate layer (Z2) with a thickness of 90 μm was removed, and one of the release sheets of the laminate sandwiched between two release sheets was laminated on the surface of the exposed intermediate layer (Z2). Also, remove the other peeling sheet, and stick the adhesive layer (X2) formed in the above (2-1) on the surface of the exposed intermediate layer (Z2), and use the substrate (Y2)/intermediate layer (Z2)/adhesive layer (X2)/heavy release film were laminated in order to produce an adhesive sheet (II).

[3] Production of adhesive laminate The peeling film of the adhesive sheet (I) produced in the above [1] was removed, and the exposed first adhesive layer (X11) was attached to the substrate (Y2) of the adhesive sheet (II) to obtain an adhesive laminate.

With regard to this adhesive laminate, peeling when the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II) is separated before and after heat treatment Forces (F ₀ ) and (F ₁ ) were measured according to the following method. As a result, peeling force (F ₀ )=0.5N/25mm, peeling force (F ₁ )=0mN/25mm, the ratio of peeling force (F ₁ ) to peeling force (F ₀ ) [(F ₁ )/(F ₀ )] is 0.

<Measurement of Peeling Force (F ₀ )> After leaving the produced adhesive laminate at 23°C and 50%RH (relative humidity) for 24 hours, the adhesive sheet (II) of the adhesive laminate was removed Attach the exposed adhesive layer (X2) to the stainless steel plate (SUS304, No. 360 grinding) of the heavy peeling film. Next, the end of the stainless steel plate to which the adhesive laminate was attached was fixed to the lower chuck of a universal tensile testing machine (product name "Tensilon UTM-4-100" manufactured by Orientec). Also, to peel off the adhesive laminate at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the base material (Y2) of the adhesive sheet (II), use the upper clamp of the universal tensile testing machine Adhesive sheet (I) for disc fixing adhesive laminate. And in the same environment as above, according to JIS Z0237:2000, the peeling force measured when peeling at the interface P at a tensile speed of 300 mm/min by the 180° tensile peeling method is taken as "peeling force (F ₀ )" .

<Measurement of Peeling Force (F ₁ )> The heavy peeling film of the adhesive sheet (II) of the produced adhesive laminate was removed, and the exposed adhesive layer (X2) was attached to a stainless steel plate (SUS304, No. 360 grinding). And the stainless steel plate and the adhesive laminate were heated at 240° C. for 3 minutes to expand the heat-expandable particles in the heat-expandable base material layer (Y1-2) of the adhesive laminate. Thereafter, in the same manner as the above-mentioned measurement of the peeling force (F ₀ ), under the above-mentioned conditions, at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), The peeling force measured when peeling was taken as "peeling force (F ₁ )". And for the measurement of the peeling force (F ₁ ), when the adhesive sheet (I) of the adhesive laminate is to be fixed on the chuck on the universal tensile testing machine, the adhesive sheet (I) will be completely separated at the interface P, When it cannot be fixed, the measurement is terminated, and the peeling force (F ₁ ) at this time is "0mN/25mm".

[Example 2] The adhesive sheet (II) in the state where the object to be processed was attached was produced by the following procedure. (1) Fixing of semiconductor wafers The light release film included in the adhesive laminate produced in Example 1 was removed, and the exposed adhesive surface of the adhesive sheet (I) of the second adhesive layer (X12) was attached to the support (glass). And the surface of the circuit surface side of the semiconductor wafer having the patterned circuit surface is attached to the adhesive layer (X2) of the adhesive sheet (II), and the adhesive laminate produced in Example 1 is interposed. , fixing the semiconductor wafer on the support body.

(2) Formation of modified area Using a stealth laser irradiation device (device name "ML300PlusWH" manufactured by Tokyo Seiki Co., Ltd.), irradiate the stealth laser from the surface opposite to the circuit formation surface of the semiconductor wafer, and form a dividing point inside the semiconductor wafer. modified area.

(3) Separation at interface P After the above (2), the adhesive laminate was heat-treated at 120° C. for 3 minutes at 120° C. or higher than the expansion start temperature (90° C.) of the heat-expandable particles. And at the interface P between the first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), it can be easily separated at one time. And after separation, the adhesive sheet (II) in the state where the semiconductor wafer forming the modified region was attached inside was obtained.

1a, 1b, 1c, 1d, 2‧‧‧adhesive laminate (I)‧‧‧adhesive sheet (X1)‧‧‧adhesive layer (X11)‧‧‧1st adhesive layer (X12)‧‧‧Second Adhesive Layer (Y1)‧‧‧Substrate (Y1-1)‧‧‧thermally expandable substrate layer (Y1-2)‧‧‧Non-expandable substrate layer (II)‧‧‧adhesive sheet (X2)‧‧‧adhesive layer (Z2)‧‧‧intermediate layer (Y2)‧‧‧Substrate 50‧‧‧Support 60, 70‧‧‧Processing objects 61‧‧‧Hardened package 61a‧‧‧Individualization of hardened packages 71‧‧‧Modified area 72‧‧‧Gap

[ Fig. 1] Fig. 1 is a schematic cross-sectional view of the adhesive laminate showing the configuration of the adhesive laminate used in the first aspect of the production method of the present invention. [ Fig. 2 ] A schematic cross-sectional view of the adhesive laminate showing the configuration of the adhesive laminate used in the second aspect of the production method of the present invention. [ Fig. 3] Fig. 3 is a schematic cross-sectional view of the adhesive laminate showing the configuration of the adhesive laminate used in the third aspect of the production method of the present invention. [ Fig. 4 ] A schematic diagram showing an example of the production method of the present invention. [ Fig. 5 ] A schematic view showing another example of the production method of the present invention.

1a, 1b‧‧‧adhesive laminate

(I)‧‧‧adhesive sheet

(X1)‧‧‧adhesive layer

(Y1)‧‧‧Substrate

(Y1-1)‧‧‧thermally expandable substrate layer

(Y1-2)‧‧‧Non-expandable substrate layer

(II)‧‧‧adhesive sheet

(X2)‧‧‧adhesive layer

(Y2)‧‧‧Substrate

P‧‧‧Interface

Claims (15)

A method of manufacturing a processed product, which is a method of manufacturing a processed product subjected to at least one of cutting and grinding using an adhesive laminate, wherein the adhesive laminate includes: a base material (Y1) and an adhesive layer (X1 ), and the substrate (Y1) has a thermally expandable adhesive sheet (I) that contains a thermally expandable substrate layer (Y1-1) of thermally expandable particles, and has a substrate (Y2) and an adhesive layer (X2) The adhesive sheet (II), which is formed by directly laminating the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II), the aforementioned manufacturing method has the following steps (1) to (3) in sequence, ‧Step (1): Attaching the surface of the adhesive layer (X1) of the above-mentioned adhesive laminate to the support, and attaching an additional object to the surface of the adhesive layer (X2) of the above-mentioned adhesive laminate ;‧Step (2): A step of applying one or more processes to the aforementioned object to be processed;‧Step (3): By heating above the thermal expansion start temperature (t) of the aforementioned thermally expandable particles, while maintaining the aforementioned object to be processed The state of being attached to the surface of the adhesive layer (X2) of the aforementioned adhesive laminate while separating the aforementioned adhesive laminate at the interface P of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) step; further, the following step (4), ‧step (4): the step of applying at least one of cutting and grinding to the surface of the object to be processed on the opposite side to the surface to which the adhesive layer (X2) is attached ; The aforementioned step (4) is implemented in at least one of the following (X) and (Y), (X): as the aforementioned one or more processing is implemented in the aforementioned step (2); (Y): in the aforementioned step ( 3) Implement later. The manufacturing method according to claim 1, wherein the thermal expansion initiation temperature (t) of the aforementioned heat-expandable particles is 60-270°C. The manufacturing method according to claim 1, wherein the substrate (Y1) of the adhesive sheet (I) has a thermally expandable substrate layer (Y1-1) and a non-thermally expandable substrate layer (Y1-2). The manufacturing method according to any one of claims 1 to 3, wherein the heat-expandable substrate layer (Y1-1) of the substrate (Y1) of the adhesive sheet (I) and the substrate (Y1-1) of the adhesive sheet (II) Y2) directly laminated. The manufacturing method according to any one of claims 1 to 3, wherein the adhesive sheet (I) has a structure in which the substrate (Y1) is sandwiched by the first adhesive layer (X11) and the second adhesive layer (X12), The first adhesive layer (X11) of the adhesive sheet (I) and the substrate (Y2) of the adhesive sheet (II) are directly laminated, the surface of the second adhesive layer (X12) of the adhesive sheet (I), It is attached to the surface of the aforementioned support. Such as the manufacturing method of claim 5, wherein the substrate (Y1) is laminated with the first adhesive The surface on the side of the adhesive layer (X11) is a surface that is easily adhered to. The manufacturing method according to any one of claims 1 to 3, wherein the surface of the substrate (Y2) on the side where the adhesive sheet (I) is laminated is the surface to be peeled off. The manufacturing method according to any one of claims 1 to 3, wherein the adhesive sheet (II) has an intermediate layer (Z2) between the substrate (Y2) and the adhesive layer (X2). The manufacturing method according to any one of claims 1 to 3, wherein the adhesive layer (X2) of the adhesive sheet (II) is an energy ray-curable adhesive layer. The manufacturing method according to any one of claims 1 to 3, wherein the adhesive sheet (II) satisfies 1 or more of the following requirements (α) to (γ), ‧requirement (α): Young’s mold of the substrate (Y2) The number is 1.0MPa or more; ‧requirement (β): the thickness of the substrate (Y2) is 5 μm or more; ‧requirement (γ): the storage modulus G' (23°C) of the adhesive layer (X2) is 0.1MPa or more. The manufacturing method according to any one of claims 1 to 3, wherein the aforementioned object to be processed is a semiconductor wafer, and the aforementioned one or more processes in the aforementioned step (2) include the following step (2-A), ‧step (2 -A): On the aforementioned semiconductor wafer, a step of forming a modified region that becomes the starting point of division; The aforementioned step (4) is the following step (4-A), ‧step (4-A): a step of grinding the surface of the aforementioned semiconductor wafer on the opposite side of the sticking surface of the adhesive layer (X2); The aforementioned step (4-A) is carried out in the following (X-A) or (Y-A), (X-A): as the aforementioned one or more processing is implemented after the aforementioned step (2-A); (Y-A): in the aforementioned step ( 3) Implement later. The manufacturing method according to any one of claims 1 to 3, wherein the aforementioned object to be processed is a semiconductor wafer, and the aforementioned one or more processes in the aforementioned step (2) include the following step (2-B), ‧step (2- B): Cover the peripheral portion of the aforementioned semiconductor chip and the aforementioned semiconductor chip on the adhesive surface of the adhesive layer (X2) with a packaging material, and harden the packaging material to obtain the aforementioned semiconductor chip packaged in a hardened packaging material. The step of hardening the package; the aforementioned step (4) is implemented in at least one of the following (X-B) and (Y-B), (X-B): as the aforementioned one or more processes, it is implemented after the aforementioned step (2-B) ; (Y-B): implemented after the aforementioned step (3). The manufacturing method according to any one of claims 1 to 3, wherein the object to be processed is a semiconductor wafer having a modified region serving as a starting point for division, The aforementioned step (4) is the following step (4-A), ‧Step (4-A): a step of grinding the surface of the aforementioned semiconductor wafer opposite to the sticking surface of the adhesive layer (X2). The manufacturing method according to any one of Claims 1 to 3, wherein the aforementioned object to be processed is a semiconductor wafer having an incision groove as a starting point for division, and the aforementioned step (1) is the following step (1-C), and the aforementioned step ( 4) It is the following step (4-C), ‧Step (1-C): attaching the surface of the adhesive layer (X1) of the aforementioned adhesive laminate to the support, and simultaneously The step of attaching the surface of the semiconductor wafer with the cut-in groove to the surface of the adhesive layer (X2); ‧Step (4-C): on the opposite side of the aforementioned semiconductor wafer to the attached surface of the adhesive layer (X2) The step of grinding the surface. An adhesive laminate for producing a processed product subjected to at least one of cutting and grinding, comprising: a substrate (Y1) and an adhesive layer (X1), and the substrate (Y1) has a layer containing heat-expandable particles The heat-expandable adhesive sheet (I) of the heat-expandable substrate layer (Y1-1), and the adhesive sheet (II) having the base material (Y2) and the adhesive layer (X2), and it is composed of the adhesive sheet ( I) is directly laminated with the substrate (Y2) of the adhesive sheet (II).

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