JP2019119208A - Manufacturing method of laminate - Google Patents

Abstract

To provide a method for efficiently manufacturing a laminate with a pattern by an adhesive piece accurately formed on an adherend while the adhesive piece is strongly bonded to the adherend.SOLUTION: A method is for manufacturing a laminate including an adherend and an adhesive piece partially covering the adherend, the adhesive piece having an adhesive force of 5 N/25 mm or more with regard to the adherend. The manufacturing method includes: a pasting step of pasting an adhesive sheet onto the adherend; a cut step of applying a cutting treatment at a boundary between a first region composing an adhesive piece and a second region not composing an adhesive piece, of the adhesive sheet; and a partial removal step of separating and removing the second region from the adherend while leaving the first region on the adherend, in this order. The partial removal step is performed before the adhesive force of the adhesive sheet to the adherend exceeds 2 N/25 mm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method of manufacturing a laminate.

  According to a laminate in which the adherend is partially covered with the adhesive piece by sticking one or more adhesive pieces to the adherend, various patterns may be formed depending on the shape and arrangement of the adhesive. Can be expressed. Thus, as a method of manufacturing a laminated body in which the adherend is partially covered with the adhesive piece with high accuracy, for example, the adhesive sheet is formed into a desired adhesive piece shape, such as coverlay film bonding of a circuit board. A method of cutting in advance and aligning and sticking the adhesive piece to an adherend is generally used. Patent document 1 is mentioned as a technical literature regarding this kind of technology.

JP, 2013-38379, A

  However, in the above-mentioned method, since the adhesive sheet is cut in advance to the desired shape of the adhesive piece and then aligned and bonded to a predetermined adherend site, an error between both the cutting accuracy and the bonding accuracy Will occur. For this reason, there is a concern that very expensive equipment will be required to manufacture products with good yield in the manufacture of electronic components that will be miniaturized and have high definition in the future. Also, for example, when the size of the cut adhesive piece is large or the shape is complicated, it may be more difficult to attach the adhesive piece to the adherend with high positional accuracy and shape accuracy. In particular, in the case of using a strongly adhesive adhesive piece to produce a highly durable laminate, the degree of difficulty in the operation of accurately adhering the adhesive piece to an adherend tends to be high.

  Therefore, an object of the present invention is to provide a method for efficiently producing a laminate in which a pattern of adhesive pieces is precisely formed on an adherend and the adhesive pieces are firmly bonded to the adherend. . Another related invention is to provide an apparatus suitable for carrying out such a manufacturing method.

  This specification provides a method for producing a laminate including an adherend and an adhesive piece partially covering the adherend, wherein the adhesive strength of the adhesive piece to the adherend is 5 N / 25 mm or more. Ru. The laminate manufacturing method comprises: attaching a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the adherend-side surface of the base material layer to the adherend; A cutting step of performing cutting processing on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece, and the second region while leaving the first region on the adherend And a partial removal step of peeling away from the adherend in the stated order. Here, the partial removal step is performed before the adhesive strength of the pressure-sensitive adhesive sheet to the adherend exceeds 2 N / 25 mm.

  According to the above manufacturing method, the first area is efficiently arranged on the adherend with high accuracy in shape and position by performing the attaching process, the cutting process and the partial removing process in this order. You can get it. In addition, since the partial removal step is performed before the adhesive force of the pressure-sensitive adhesive sheet to the adherend exceeds 2 N / 25 mm, the second region can be easily peeled off from the adherend, and deformation of the adherend or deformation of the adherend Damage is also less likely to occur.

  In some embodiments, as the above-mentioned pressure-sensitive adhesive sheet, one having an adhesion of 2 N / 25 mm or less after 24 hours at 23 ° C. after bonding to polyimide can be preferably used. According to such a pressure-sensitive adhesive sheet, it is possible to flexibly cope with the lead time of the manufacturing process of the laminate.

  In some embodiments of the laminate manufacturing method disclosed herein, heat treatment is performed after the partial removal step to make the adhesion of the first region to the adherend 5 N / 25 mm or more. This embodiment includes, for example, a pressure-sensitive adhesive layer including a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B which is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer. Although it can implement using an adhesive sheet, it is not limited to this.

  In some embodiments, the monomer component that makes up the polymer A may include N-vinyl cyclic amide. As described above, a pressure-sensitive adhesive sheet using a polymer A having a composition containing N-vinyl cyclic amide as a constituent monomer component can exhibit a good adhesion increasing property, and thus is preferably used for the practice of the manufacturing method disclosed herein. obtain.

  In some other embodiments of the laminate manufacturing method disclosed herein, ultraviolet irradiation treatment is performed after the partial removal step to make the adhesion of the first region to the adherend 5 N / 25 mm or more. . This embodiment is made of, for example, a photocurable composition containing a base polymer and a photocuring agent, the photocuring agent is a polyfunctional (meth) acrylate, and the content of the photocuring agent is 100% by weight of the base polymer. Although it can implement using the adhesive sheet provided with the adhesive layer which is 1 weight part or more and 50 weight parts or less with respect to a part, it is not limited to this.

In addition, after the partial removal step, the laminate manufacturing method disclosed herein is carried out in an aspect of storing at normal temperature until the adhesion of the first region to the adherend becomes 5 N / 25 mm or more. It is also good.
In this specification, normal temperature means a temperature of about 0 ° C. to 35 ° C., typically 10 ° C. to 35 ° C., unless otherwise specified.

  In some embodiments, as the pressure-sensitive adhesive sheet, a sheet having a thickness of 30 μm or more and a thickness Ts of the base layer of 2 or more times the thickness Ta of the pressure-sensitive adhesive layer may be preferably used. . By using such a pressure-sensitive adhesive sheet, it is possible to obtain an advantage of being able to easily perform the attaching operation to the adherend and the peeling operation of the second region.

  The second region is preferably set such that at least one end thereof reaches the end of the pressure-sensitive adhesive sheet. This has the advantage that it is easier to pick up the second region when performing the partial removal step. The second region may have a shape in which one end reaching the end of the pressure-sensitive adhesive sheet becomes wider toward the end of the pressure-sensitive adhesive sheet from the viewpoint of improving the pickup performance.

The manufacturing method disclosed here can be preferably implemented in the aspect which uses the adhesive sheet which is 2500 cm < ² > or more in area, and whose length of a short side is 50 cm or more to the said sticking process. In the embodiment using such a large-area and wide-width adhesive sheet, the advantages of adopting the manufacturing method disclosed herein can be exhibited more effectively.

  The manufacturing method disclosed herein uses, as the pressure-sensitive adhesive sheet and the adherend used in the sticking step, one including a plurality of units corresponding to the laminate, and as a step performed after the sticking step, You may further include the division process which divides the said adhesive sheet and the said to-be-adhered body into the said unit. A plurality of laminates can be efficiently manufactured by dividing the pressure-sensitive adhesive sheet including a plurality of units as described above after attaching it to an adherend. The configuration of the plurality of units may be identical or different.

  According to this specification, an apparatus is provided for producing a laminate including an adherend and an adhesive strip partially laminated to the adherend. The apparatus includes a sticking mechanism for sticking a pressure-sensitive adhesive sheet. In addition, the device may include a cutting mechanism for cutting the pressure-sensitive adhesive sheet. Also, the device may include a peeling mechanism that peels the second region. Any of the laminate manufacturing methods disclosed herein can be suitably implemented using a manufacturing apparatus having such a configuration.

  A combination of the above-described elements as appropriate may also be included in the scope of the invention for which protection by a patent is sought by the present patent application.

It is a flowchart which shows the laminated body manufacturing method which concerns on one Embodiment. It is a perspective view showing the layered product manufactured by the layered product manufacturing method concerning one embodiment. It is the III-III sectional view taken on the line of FIG. It is a perspective view explaining the cutting process of the laminated body manufacturing method which concerns on one Embodiment. It is an explanatory view showing a schematic structure of a layered product manufacturing device used for a layered product manufacturing method concerning one embodiment. It is explanatory drawing which shows the implementation method of a durability test.

Hereinafter, preferred embodiments of the present invention will be described. Matters other than the matters specifically mentioned in the present specification and necessary for the practice of the present invention are based on the teaching of the practice of the invention described in the present specification and the common general knowledge at the time of filing. It can be understood by the vendor. The present invention can be implemented based on the contents disclosed in the present specification and common technical knowledge in the field.
In the following drawings, the same reference numerals may be given to members / parts having the same function, and overlapping descriptions may be omitted or simplified. Also, the embodiments described in the drawings are schematically illustrated in order to clearly explain the present invention, and the actual sizes and scales are not necessarily accurately represented.

<< Production method of laminates >>
FIG. 1 is a flowchart showing a method of manufacturing a laminate according to an embodiment, FIG. 2 is a perspective view showing a laminate manufactured by the method, and FIG. 3 is a cross-sectional view along line III-III. It is. As shown in FIGS. 2 and 3, the laminate 1 manufactured according to this embodiment includes an adherend 10 and adhesive pieces 21A and 21B partially covering the surface 10A of the adherend 10. After sticking the adhesive sheet 20 to the adherend 10, the adhesive pieces 21A and 21B leave the first region 21 of the adhesive sheet 20 on the adherend 10 and leave the second region 22 from the adherend 10 By peeling and removing, it is formed from the first region 21 left on the adherend 10. The pressure-sensitive adhesive sheet 20 has a configuration in which the pressure-sensitive adhesive layer 204 is laminated on one side of the base material layer 202.

The laminate manufacturing method according to this embodiment includes, as shown in FIG. 1, a sticking step S10, a cutting step S20, and a partial removing step S30 in this order.
In the sticking step S10, the pressure-sensitive adhesive sheet 20 is attached to the adherend 10. The pressure-sensitive adhesive sheet 20 used in this step does not constitute the first region 21 which is a region included in the components of the laminate 1 as the adhesive pieces 21A and 21B, and does not constitute the components of the laminate 1. And a second region 22 used only in the manufacturing process of In the example shown in FIG. 2, a second region 22 extending linearly from one end in the longitudinal direction of the pressure-sensitive adhesive sheet 20 to the other end is set substantially at the center of the width of the pressure-sensitive adhesive sheet 20. In the adhesive sheet 20 used for sticking process S10, the 1st area | region 21 and the 2nd area | region 22 are physically connected, and these area | regions 21 and 22 can be handled as a series of adhesive sheet 20. As shown in FIG.

In the cutting step S20, the boundary between the first area 21 and the second area 22 of the pressure-sensitive adhesive sheet 20 attached to the adherend 10 is cut. For example, as shown in FIG. 4, laser cutting is performed by irradiating the laser light L along a planned cutting line C that forms the boundary between the first area 21 and the second area 22. Although FIG. 4 shows an example of laser cutting, the means for cutting is not particularly limited, and can be appropriately selected from various known cutting means according to the purpose and application. Examples of such cutting means include laser cutting using laser light such as a CO ₂ laser or YAG laser; cutting with a blade such as a Thomson blade, pinnacle blade, rotary blade or knife; blade cutting; It is not limited to these. The cutting means can be used singly or in combination of two or more.

  In the partial removal step S30, before the adhesion of the pressure-sensitive adhesive sheet attached to the adherend in the attachment step to the adherend exceeds 2 N / 25 mm (in other words, the adhesion after attachment is 2 N / 25 mm or less) While being held down). In the partial removal step S30, the second region 22 is peeled and removed from the adherend 10 while leaving the first region 21 on the adherend 10. For example, the second region 22 is peeled off from one end in the longitudinal direction of the adhesive sheet 20 to the other end. As a result, as shown in FIGS. 2 and 3, the adhesive pieces 21A and 21B formed from the first region 21 are disposed on the adherend 10 separately from each other, and the adhesive pieces 21A and 21B are adhered to each other. A structure in which the adherend 10 is exposed is formed.

  In the laminate manufacturing method according to this embodiment, after the pressure-sensitive adhesive sheet 20 is attached to the adherend 10, a part of the pressure-sensitive adhesive sheet 20, that is, the second region 22 is peeled off from the adherend 10. A covering pattern consisting of two adhesive pieces 21A and 21B disposed apart from each other is formed on the adherend 10. According to this method, the first region 21 constituting the two adhesive pieces 21A and 21B separated from each other in the laminate 1 can be attached to the adherend 10 in the form of one adhesive sheet 20, and the adhesive Since the adjustment of the relative positional relationship between the adhesive pieces 21A and the adhesive pieces 21B becomes unnecessary when the sheet 20 is attached, the manufacturing efficiency of the laminate 1 is improved. In addition, since the boundary between the first region 21 and the second region 22 of the pressure-sensitive adhesive sheet 20 is cut after the pressure-sensitive adhesive sheet 20 is attached to the adherend 10, the shape accuracy of the first region 21 and the adherend It is easy to improve the position accuracy with respect to 10. For example, in the case where the adhesive sheet 20 is slightly misaligned in the affixing position of the adhesive sheet 20 to the adherend 10 in the adhering step S10, or when the adhesive sheet 20 is slightly expanded or deformed due to temperature change or release of internal stress Also, by adjusting the position and shape of the cutting process in the cutting step S20, the influence thereof can be eliminated or reduced.

  In the above-described manufacturing method, the laminate 1 in which the adhesive strength of the adhesive pieces 21A and 21B to the adherend is 5 N / 25 mm or more is manufactured. The fact that the adhesive pieces 21A and 21B are firmly joined to the adherend 10 means that an external force such as contact of human hands, deformation of the adherend, or a laminate occurs when the laminate 1 is used. Is preferable from the viewpoint of suppressing an event in which the adhesive pieces 21A and 21B peel off or float from the adherend 10 due to environmental factors such as being exposed to wind and rain or temperature change. On the other hand, in the partial removal step S30, if the adhesiveness of the second region 22 to the adherend 10 is too high, damage such as deformation or surface peeling occurs in the adherend 10 when the second region 22 peels off. In addition, inconveniences such as breakage of the second region 22 during peeling may occur. According to the above manufacturing method, the adhesive strip 21A is implemented by performing the partial removal step S30 before the adhesive force of the pressure-sensitive adhesive sheet attached to the adherend in the attachment step S10 to the adherend exceeds 2N / 25 mm. , 21B can be manufactured firmly to the adherend 10, and the above-mentioned problems can be avoided or reduced in the partial removal step S20.

In some embodiments, the adhesive force A _P to the adherend of the adhesive sheet at the time of partial removal step, from the viewpoint of peeling easiness of the second region, for example, may be less than 2N / 25 mm, 1.5 N / It may be less than 25 mm, may be 1.3 N / 25 mm or less, may be 1 N / 25 mm or less, and may be 0.8 N / 25 mm or less. The lower limit of the adhesive strength A _P is not particularly limited, from the viewpoint of suppressing the positional deviation and the floating of the first region in the cutting process and some removal step, for example. It may be 0.005 N / 25 mm or more, 0.01 N / 25 mm or more, 0.05 N / 25 mm or more, 0.1 N / 25 mm or more, 0.2 N / 25 mm or more.

The manufacturing method disclosed herein uses a pressure-sensitive adhesive sheet having an adhesive strength (hereinafter also referred to as an adhesive strength after room temperature 24 hours) after 24 hours at 23 ° C. after bonding to a polyimide is 2N / 25 mm or less Can be implemented preferably. According to such a pressure-sensitive adhesive sheet, it is possible to flexibly cope with the lead time of the manufacturing process of the laminate. The upper limit of the room temperature 24 hours after adhesion can be, for example, comparable to the one of the upper limit of the adhesive strength A _P exemplified above. The lower limit of the room temperature 24 hours after adhesion can be, for example, comparable to the one of the lower limit of the adhesive strength A _P exemplified above.

  After the partial removal step S30 is performed, an adhesive strength increase step S40 may be further performed to enhance the adhesive strength of the adhesive pieces 21A and 21B to the adherend 10, if necessary. According to the manufacturing method including the adhesive strength raising step, it is possible to shorten the time until obtaining the desired laminate (that is, the laminate having the adhesive strength of the adhesive piece to the adherend of 5 N / 25 mm or more). This can improve the productivity of the laminate. Moreover, it is in the tendency for a layered product with higher adhesive power to the adherend of an adhesive piece to be manufactured by performing the above-mentioned adhesive power increase process.

  Adhesion strength increase process S40 may be a process of giving stimulation which promotes the rise of adhesion power of adhesion pieces 21A and 21B. The content of the above-mentioned stimulation can be suitably selected according to the type etc. of an adhesive sheet to be used. Examples of the stimulation may include heating, irradiation with actinic radiation, pressing (pressurization) and the like. These stimuli can be applied singly or in combination of two or more.

  In the laminate manufacturing method disclosed herein, the adhesive strength increasing step is not an essential step, but the type of adhesive sheet to be used, the productivity and performance of the desired laminate, and the equipment and cost for manufacturing the laminate. It is an optional process that can be adopted appropriately in consideration of For example, by appropriately selecting the pressure-sensitive adhesive sheet used for producing the laminate, the pressure-sensitive adhesive sheet to the adherend has an adhesive strength of more than 2 N / 25 mm even in an embodiment where the special pressure-sensitive adhesive increase step is not performed after the partial removal Partially removing the adhesive sheet, and a laminate having an adhesive strength of 5 N / 25 mm or more to the adherend of the pressure-sensitive adhesive sheet can be produced.

  The adhesive strip contained in the laminate produced by the method disclosed herein includes a base material layer and an adhesive layer, and is bonded to the adherend via the adhesive layer. Thus, in the obtained laminate, the adhesive piece and the adherend are joined by the adhesive, that is, the adhesive maintains the desired viscoelasticity by the method disclosed herein. It is preferable from the viewpoints of flexibility, impact resistance, stress relaxation property, low temperature characteristics, adhesion between an adherend and an adhesive piece of a laminate to be produced, and the like.

  In the example shown in FIG. 2, the adhesive sheet 20 having substantially the same size as the adherend 10 is attached so as to cover the entire surface (entire area) of one side of the adherend 10. The sticking aspect of an adhesive sheet is not limited to this. For example, the pressure-sensitive adhesive sheet may be attached so as to cover only a partial region on one side of the adherend, or a part of the pressure-sensitive adhesive sheet may be attached so as to protrude from the adherend. In addition, in the pressure-sensitive adhesive sheet used in the sticking step S10, the first region and the second region may be connected to such an extent that they can be handled as a continuous sheet. It is not hindered that a cutting aid structure such as a cut (a perforation or the like) or a half cut is provided at the boundary between the two areas. Here, the half cut means a cut whose depth does not penetrate the adhesive sheet in the thickness direction, and is typically formed as a cut whose depth does not penetrate the base material layer in the thickness direction. Such a cut can be formed, for example, by advancing the processing blade from the back surface of the base layer (the side opposite to the side on which the pressure-sensitive adhesive layer is laminated) to a depth not penetrating the base layer. In one aspect, a pressure-sensitive adhesive sheet in which a cutting assistance structure is not provided at the boundary between the first region and the second region can be preferably used from the viewpoint of improving the handleability of the pressure-sensitive adhesive sheet and reducing the manufacturing cost. Moreover, the adhesive sheet used at sticking process S10 may be provided with the mark which helps the position alignment with this adhesive sheet and a to-be-adhered body. The mark may be a structural mark such as a through hole, a notch, a recess or the like, or may be a visual mark by an optically detectable marking (eg, printing or coloring) , Arrangement of different members (for example, application of an identification label, fixation of an element enabling transmission or reflection of a signal). Such a mark may be provided in one or both of the first area and the second area, and may be provided at the boundary between the first area and the second area.

  Further, in the example shown in FIG. 4, in the cutting step S20, continuous linear cutting is performed at a depth which penetrates the pressure-sensitive adhesive sheet and reaches the adherend surface, but the aspect of the cutting is limited to this. I will not. For example, the first region and the second region after the cutting step S20 may be partially connected to the extent that the partial removal step S30 can be appropriately performed. Examples of such cutting processing include discontinuous cutting processing such as perforations, half cutting, processing combining perforations and half cutting (for example, cuts passing through the substrate layer, and the substrate layer Cutting with an aspect in which incisions of a depth not to be penetrated alternately repeat, and the like. In addition, the cutting process may be performed at a depth that penetrates the pressure-sensitive adhesive sheet to the surface of the adherend, and passes through the pressure-sensitive adhesive sheet so that the depth further partially extends from the surface of the adherend. It may be performed at a depth which does not penetrate the pressure-sensitive adhesive sheet (i.e., half cut). In the manufacturing method disclosed herein, since the adhesion of the pressure-sensitive adhesive sheet to the adherend is suppressed to a low level when performing the partial removal step S30, the first region at least deep enough to penetrate the base material layer It is preferable to perform cutting so that the second region and the second region are completely separated. This can be advantageous from the viewpoint of improving the pickup performance of the second region in the partial removal step S30, preventing floating or shifting of the first region, improving the outer shape accuracy of the first region, and the like.

  In the example shown in FIG. 4, one end and the other end of the linearly extending second region reach the end of the pressure-sensitive adhesive sheet. Setting the second area so that at least one end of the second area reaches the end of the pressure-sensitive adhesive sheet in this manner is preferable from the viewpoint of the pickup property of the second area in the partial removal step S30. In a mode in which the second area does not reach the end of the adhesive sheet, for example, the second area is picked up by sticking and pulling up a strong adhesive tape on the back of the second area at one end of the second area. Can. Such a pickup method can also be adopted in a mode in which at least one end of the second region reaches the end of the adhesive sheet. In the laminate manufacturing method disclosed herein, the adhesive force of the adhesive sheet to the adherend at the time of the partial removal step is 2N / 25 mm or less by the method of sticking and pulling up the adhesive tape as described above. It is advantageous from the viewpoint of the pickup performance improvement of the second region.

  In an aspect in which the second region is set to reach the end of the pressure-sensitive adhesive sheet, the width of the second region to the end of the pressure-sensitive adhesive sheet is preferably 0.2 mm or more from the viewpoint of pick up property It may be 0.5 mm or more, or 1 mm or more. In order to enhance the pick-up property, the width of the second area may be increased near the end of the adhesive sheet. Further, from the viewpoint of miniaturizing a product (such as an electronic device) including the laminate obtained by the manufacturing method disclosed herein, the width of the second region to the end of the pressure-sensitive adhesive sheet may be 10 mm or less Preferably, it is more preferably 8 mm or less.

When the laminate manufacturing method disclosed herein includes the step of increasing the adhesion, the degree to which the adhesion is increased in the step is not particularly limited, and the adhesion after the step or the adhesion after the step is higher than the adhesion before the step. The adhesion of the laminate obtained through the process may be relatively high. In some embodiments, the step of increasing the adhesive strength comprises the adhesive strength A ₀ [N / 25 mm] to the adherend before the process and the adhesive power A ₁ [N / 25 mm] to the adherend after the process It is preferable to carry out the relationship with to satisfy the ratio (A ₁ / A ₀ ) ≧ 2. That is, it is preferable to raise the adhesive force with respect to the to-be-adhered body of an adhesive sheet to 2 times or more before this process at an adhesive force raise process. According to such an adhesive strength increase step, the ease of removal of the second region in the partial removal step and the strong adhesiveness of the adhesive piece to the adherend in the manufactured laminate tend to be both compatible. In some embodiments, the ratio (A ₁ / A ₀ ) may be, for example, 3 or more, 5 or more, or 10 or more. Although the upper limit of the above ratio (A ₁ / A ₀ ) is not particularly limited, it is usually 10000 or less, 5000 or less or 2000 or less from the viewpoint of suppressing positional deviation or floating of the first region before the adhesive strength increasing step. Is preferred. Each of the adhesive strengths A ₀ and A ₁ is an adherend of a pressure-sensitive adhesive sheet at a peeling angle of 180 degrees and a tensile speed of 300 mm / min in an environment of 23 ° C. and 50% RH according to JIS Z0237. It can grasp by measuring the exfoliation strength from.

Adhesion A ₀ to adherends of the adhesive sheet before adhesion increasing step may be, for example, approximately the same extent as the adhesive force A _P at the portion removing step. Therefore, the upper limit value and the lower limit value of the adhesive force A _P illustrated above are each independently, it may also be applied to each of the upper and lower limit values which can be taken of the adhesion A _0. Each upper and lower limits of adhesion A _P illustrated above is independently, can be applied to each of the upper and lower limit values which can be taken in the initial adhesive strength B ₀ to be described later.

In the laminate produced by the method disclosed herein, the adhesive force _AF of the adhesive piece to the adherend may be, for example, more than 5 N / 25 mm, may be 7 N / 25 mm or more, or 10 N / 25 mm or more. , 12 N / 25 mm or more may be sufficient. It is preferable from the viewpoint of suppressing peeling and floating of the adhesive piece from the adherend during use of the laminate that the adhesive strength _AF is high. The upper limit of the adhesive force _AF is not particularly limited. From the viewpoint of facilitating compatibility with the peelability of the second region in the partial removal step, in some embodiments, the adhesive force _AF may be, for example, 50 N / 25 mm or less, or 40 N / 25 mm or less. , 35 N / 25 mm or less, or 30 N / 25 mm or less.

In the embodiment including the adhesion raising step, the adhesion A ₁ [N / 25 mm] of the adhesive sheet to the adherend after the adhesion raising step is, for example, the adherend of the adhesive piece in the manufactured laminate. generally it may be the same extent as the adhesive force a _F against. Therefore, the upper limit value and the lower limit value of the adhesive force A _F illustrated above are each independently, it may also be applied to each of the upper and lower limit values which can be taken of the adhesion A _1. Each upper and lower limits of adhesion A _F illustrated above are each independently, it may also be applied to each of the possible upper limit value and the lower limit value of the stimulation after adhesion B ₁ to be described later.

The content of the stimulus given to the adhesive sheet in the adhesion raising step is, for example, an adhesion increase ratio (B ₁ / B) defined as a ratio of initial adhesion B ₀ to adhesion to polyimide of adhesive sheet used and adhesion B ₁ after stimulation. ₀ ) can be set to satisfy a predetermined target value. Initial adhesion B ₀ and after stimulation adhesion B ₁ represents, is measured by the method described in the examples below.

In the case where the manufacturing method disclosed herein includes an adhesion increasing step, the adhesion increasing step is preferably performed such that the adhesion increase ratio (B ₁ / B ₀ ) is, for example, 2 or more, and the adhesion increase is It is more preferable to carry out such that the ratio (B ₁ / B ₀ ) is 3 or more, 5 or more, 10 or more, or 15 or more. Also. From the viewpoint of reducing the load on the adhesive sheet and the adherend and improving the productivity of the laminate, the adhesive strength increasing step has an adhesive strength increase ratio (B ₁ / B ₀ ) of about 10000 or less, 5000 or less or 2000 or less To be implemented. In some embodiments, the adhesion increase ratio (B ₁ / B ₀ ) may be, for example, 1000 or less, 500 or less, 200 or less, or 100 or less.

In flexible display panels, flexible printed wiring boards (FPCs), devices in which a display panel and a wiring board are integrated, flexible substrate materials are used, and from the viewpoint of heat resistance and dimensional stability, A polyimide film is often used as a substrate material. A pressure-sensitive adhesive sheet exhibiting the above-mentioned tackiness B ₀ , B ₁ or tackiness increase ratio (B ₁ / B ₀ ) with respect to polyimide is used in the production of a laminate in a mode in which polyimide is used as an adherend. In the part removing step, the peeling workability of the second region is good, and when using the obtained laminate, it is possible to exert the property of being excellent in the adhesion reliability with the adherend. By utilizing such properties, the film cover lay of the FPC can be formed accurately and efficiently. Thus, the methods disclosed herein can be preferably applied, for example, to the manufacture of FPCs with film cover lays.

  The heating temperature in the case of heating as a stimulus given to the adhesive sheet in the adhesive strength raising step is not particularly limited, and the workability, economy, heat resistance of the substrate layer and adherend that may be included in the adhesive sheet, etc. Can be set. The heating temperature may be, for example, less than 150 ° C., 120 ° C. or less, 100 ° C. or less, 80 ° C. or less, or 70 ° C. or less. The heating temperature may be, for example, 40 ° C. or more, 50 ° C. or more, or 60 ° C. or more, may be 80 ° C. or more, or 100 ° C. or more. With higher heating temperatures, the tack can be increased by a shorter treatment. The heating time is not particularly limited, and may be, for example, 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less. Alternatively, the heat treatment may be performed for a longer period of time (for example, 2 hours or more, 5 hours or more, or the like) as long as significant heat deterioration does not occur in the adhesive sheet or the adherend. Note that the heat treatment may be performed at one time or may be performed plural times.

  The pressure-sensitive adhesive sheet used in the sticking step may include only one region (first region) to be a pressure-sensitive adhesive piece constituting the laminate in a single pressure-sensitive adhesive sheet, for example, as shown in FIG. It may include two first regions separated from each other, and may include three or more first regions. When the adhesive sheet includes a plurality of first regions, the shape of the first regions may be the same or different. Similarly, the pressure-sensitive adhesive sheet used in the sticking step may include only one second region to be peeled and removed in the partial removal step, for example, as shown in FIG. 4 in a single pressure-sensitive adhesive sheet. And may contain two or more or three or more. When one adhesive sheet includes a plurality of second regions, the shapes of the second regions may be the same or different.

  In the laminate manufacturing method according to some embodiments, as the pressure-sensitive adhesive sheet and the adherend used in the sticking step, those including a plurality of units corresponding to the laminate manufactured by the method can be used. The aspect may further include a dividing step of dividing the pressure-sensitive adhesive sheet and the adherend into the units as a step performed after the attaching step. The dividing step can be performed at any time after the sticking step. For example, by performing the dividing step after at least the cutting step, the cutting step can be performed collectively on a plurality of units. The manufacturing method disclosed herein can be carried out, for example, in a mode including the above-mentioned dividing step between (a) cutting step and partial removing step. In the manufacturing method including the adhesion raising step after the partial removal step, the aspect including the division step, for example, between (b) the partial removal step and the adhesion raising step or after (c) the adhesion raising step It may be implemented in One or more of the embodiments (a) to (c) may be combined. In addition, the said aspect (a) may be preferably implemented, for example using the adhesive sheet provided with the adhesive layer (2) mentioned later. The said aspect (b) and said aspect (c) may be preferably implemented, for example using the adhesive sheet provided with the adhesive layer (1) or adhesive layer (2) mentioned later.

<< Manufacturing Equipment >>
For example, as shown in FIG. 5, the laminated body manufacturing method disclosed herein includes a sticking mechanism 51 that sticks the pressure-sensitive adhesive sheet 20 to the adherend 10, and the first area 21 and the second area 22 of the pressure-sensitive adhesive sheet 20. A laminate manufacturing apparatus 50 comprising: a cutting mechanism 52 for performing cutting processing at the boundary; and a peeling mechanism 53 for peeling and removing the second region 22 from the adherend 10 while leaving the first region 21 on the adherend 10 Can be implemented using

  The sticking mechanism 51 is configured to be able to carry out the sticking step in any of the manufacturing methods disclosed herein, and includes, for example, an adherend supply means, an adhesive sheet supply means, and a pressure bonding means to the adherend of the adhesive sheet. , Etc. may include one or more. The cutting mechanism 52 is configured to perform the cutting step in any of the manufacturing methods disclosed herein, and may include one or more of the cutting means as exemplified above. The peeling mechanism 53 is configured to be able to carry out the partial removal step in any of the methods disclosed herein, and, for example, one or more of pickup means, holding means, peeling means, etc. of the second region. May be included.

In addition, the laminated body manufacturing apparatus which may be used for implementation of the laminated body manufacturing method of the aspect containing an adhesive force raise process raises the adhesive force which is not shown in figure as a mechanism which gives the stimulus which raises the adhesive force with respect to 1st area | region. It may further include a mechanism. The adhesion raising mechanism is configured to perform an adhesion raising step in any of the methods disclosed herein by providing a stimulus that can increase the adhesion of the adhesive sheet to the adhesive sheet. ing. The adhesion raising mechanism includes, for example, one or more of UV irradiation means (UV irradiation lamp, mirror for light path adjustment, etc.), heating means (warm air heater, infrared heater, electric heater etc.), pressing means, etc. obtain.
Moreover, the manufacturing apparatus used for the laminated body manufacturing method of the aspect containing a division | segmentation process may further include the division mechanism which is not shown in figure. The dividing mechanism may be configured to carry out the dividing step using known dividing means such as cutting with a Thomson blade, pinnacle blade, rotary blade, knife or the like, or laser cutting, water jet cutting, blade cutting, etc. it can.

<< Adhesive sheet >>
The following will describe some examples of pressure-sensitive adhesive sheets that can be preferably adopted to carry out the laminate manufacturing method disclosed herein, but are not intended to limit the scope of the present invention.

  The laminate production method disclosed herein can be preferably practiced using a pressure-sensitive adhesive sheet having a configuration including a base material layer and a pressure-sensitive adhesive layer laminated on at least the adherend side of the base material layer. According to the pressure-sensitive adhesive sheet having a configuration in which the pressure-sensitive adhesive layer is laminated on the base material layer, the pressure-sensitive adhesive layer can be reinforced by the base material layer, so the second region is easily peeled off from the adherend in the partial removal step.

<Base layer>
Various film substrates can be preferably used as the substrate layer. The film substrate may be a porous substrate such as a foam film or a non-woven sheet, or may be a non-porous substrate, and a base having a structure in which a porous layer and a non-porous layer are laminated. It may be a material. In some embodiments, it is preferable to use, as the film substrate, one including a resin film that can be independently maintained in shape (self-supporting or independent) as a base film. Here, "resin film" means a non-porous structure and a resin film which is substantially free of bubbles (voidless). Therefore, the said resin film is the concept distinguished from a foam film and a nonwoven fabric. The resin film may have a single layer structure or a multilayer structure of two or more layers (for example, a three-layer structure).

  Examples of the resin material constituting the resin film include polyester, polyolefin, nylon 6, nylon 66, polyamide (PA) such as partially aromatic polyamide, polyimide (PI), polyamide imide (PAI), polyetheretherketone (PEEK) ), Fluorine resin such as polyether sulfone (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene (PTFE), acrylic resin And resins such as polyacrylate, polystyrene, polyvinyl chloride and polyvinylidene chloride can be used.

  The resin film may be formed of a resin material containing one kind of such a resin alone, or may be formed of a resin material in which two or more kinds are blended. Good. The resin film may be unstretched or may be stretched (for example, uniaxially stretched or biaxially stretched). For example, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, non-oriented polypropylene (CPP) film, biaxially oriented polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) ), And resin films such as PP / PE blend films can be preferably used. PET film, PEN film, PPS film and PEEK film are mentioned as an example of a preferable resin film from the viewpoint of strength and dimensional stability. PET films and PPS films are particularly preferable from the viewpoint of availability and the like, and PET films are particularly preferable.

  For resin films, known as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, antiblocking agents, etc. to the extent that the effects of the present invention are not significantly impaired. The additives of the above can be blended as needed.

  The method for producing the resin film is not particularly limited. For example, conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die cast molding, calendar roll molding and the like can be appropriately adopted.

  The base layer may be substantially composed of such a base film. Alternatively, the base layer may include an auxiliary layer in addition to the base film. Examples of the auxiliary layer include an optical property adjusting layer (for example, a colored layer, an antireflection layer), a print layer or a laminate layer for giving a desired appearance to the base material layer, an antistatic layer, an undercoat layer, peeling. Surface treatment layers, such as a layer, are mentioned.

  On the side of the base layer on which the pressure-sensitive adhesive layer is to be laminated, an undercoat layer by corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of an undercoating agent (primer), as necessary. A conventionally known surface treatment such as the formation of the above may be applied. Such surface treatment may be treatment to improve the anchorability of the pressure-sensitive adhesive layer to the base material layer. The composition of the primer used to form the undercoat layer is not particularly limited, and can be appropriately selected from known ones. The thickness of the undercoat layer is not particularly limited, but is usually about 0.01 μm to 1 μm, and preferably about 0.1 μm to 1 μm. Examples of other treatments that may be applied to the base material layer as required include antistatic layer formation treatment, colored layer formation treatment, and printing treatment. These treatments can be applied alone or in combination.

<< Adhesive layer >>
The composition of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited. The pressure-sensitive adhesive is an acrylic polymer, rubber-based polymer, polyester-based polymer, urethane-based polymer, polyether-based polymer, silicone-based polymer, polyamide-based polymer, fluorine-based polymer, etc. One or two or more of various polymers exhibiting elasticity may be contained as a base polymer (the main component in the polymer component, that is, the component that occupies more than 50% by weight). Among them, acrylic pressure-sensitive adhesives and rubber pressure-sensitive adhesives are exemplified as preferable pressure-sensitive adhesives. Here, the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing an acrylic polymer as a base polymer. The same applies to rubber pressure-sensitive adhesives. The above-mentioned acrylic polymer refers to a polymer in which 50% by weight or more of the total amount of monomer components constituting the acrylic polymer is an acrylic monomer. In the present specification, an acrylic monomer refers to a monomer having at least one (meth) acryloyl group in one molecule. Moreover, the (meth) acryloyl group is a meaning that comprehensively indicates an acryloyl group and a methacryloyl group.

  Some examples of the pressure-sensitive adhesive layer that can be preferably used in the manufacturing method disclosed herein include (1) a pressure-sensitive adhesive layer containing a base polymer and a siloxane structure-containing polymer (hereinafter also referred to as "pressure-sensitive adhesive layer (1)" And (2) a pressure-sensitive adhesive layer (hereinafter, also referred to as "pressure-sensitive adhesive layer (2)") formed of a photocurable composition containing a base polymer and a photo-curing agent. Hereinafter, although an adhesive layer (1) and an adhesive layer (2) are demonstrated in detail, the adhesive sheet used for the manufacturing method disclosed here is not limited to what has these adhesive layers.

<Pressure-sensitive adhesive layer containing base polymer A and siloxane structure-containing polymer B>
The pressure-sensitive adhesive layer (1) contains a base polymer A and a siloxane structure-containing polymer B, and after being bonded to an adherend, the adhesion is kept low for a while in a room temperature region (for example, 20 ° C. to 30 ° C.) Aging (which may be heating, aging, a combination thereof, and the like) may exhibit a property that adhesion is greatly increased. Therefore, it can be preferably used for the laminate manufacturing method disclosed herein. The pressure-sensitive adhesive layer (1) can be formed from a pressure-sensitive adhesive composition containing a base polymer A or a precursor thereof and a siloxane structure-containing polymer B. The form of the pressure-sensitive adhesive composition is not particularly limited, and may be various forms such as, for example, water dispersion type, solvent type, hot melt type, actinic ray curable type (for example, UV curable type).

(Base polymer A)
An acrylic polymer can be preferably used as the base polymer A (hereinafter sometimes abbreviated as "polymer A") of the pressure-sensitive adhesive layer (1). When an acrylic polymer is used as the polymer A, good compatibility with the polymer B tends to be easily obtained. The good compatibility between the polymer A and the polymer B is due to the improvement of the mobility of the polymer B in the pressure-sensitive adhesive layer, the low tackiness in the partial removal step and the strong tackiness after the tackiness increase treatment (for example, heat treatment) It is preferable because it can contribute to the realization of the pressure-sensitive adhesive layer (1) having a combination of Preferably, 50% by weight or more of the pressure-sensitive adhesive layer (1) is an acrylic polymer.

As the acrylic polymer, for example, one in which 40% by weight or more of the total amount of monomer components constituting the acrylic polymer is (meth) acrylic acid alkyl ester can be preferably used. As the (meth) acrylic acid alkyl ester, one having a linear or branched alkyl group having 1 to 20 carbon atoms (that is, _C1-20 ) at the ester end may be preferably used. The proportion of (meth) acrylic acid C _1-20 alkyl ester in the total constituent monomer components of the acrylic polymer may be, for example, 50% by weight or more, or 55% by weight or more because of easy balance of properties. And 60% by weight or more. For the same reason, the proportion of (meth) acrylic acid C _1-20 alkyl ester in the total amount of constituent monomer components may be, for example, 99.9% by weight or less, 98% by weight or less, or 95% by weight or less Good. In some embodiments, the proportion of (meth) acrylic acid C _1-20 alkyl ester in the total amount of monomer components may be, for example, 90% by weight or less, 85% by weight or less, or 80% by weight or less.

Non-limiting specific examples of (meth) acrylic acid C _1-20 alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate ( (Meth) acrylate n-butyl, (meth) acrylate isobutyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) Neopentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (meth) ) Isononyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, ( Ta) Undecyl acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotridodecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, Heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate and the like can be mentioned.

Among these, it is preferable to use at least (meth) acrylic acid C _1-18 alkyl ester, and it is more preferable to use at least (meth) acrylic acid C _1-14 alkyl ester. In some embodiments, the constituent monomer component of the acrylic polymer is selected from (meth) acrylic acid _C4-12 alkyl esters (preferably acrylic acid _C4-10 alkyl esters such as acrylic acid _C6-10 alkyl esters) Can include at least one of For example, acrylic polymers comprising one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) are preferred, and acrylic polymers comprising at least 2EHA are particularly preferred. Examples of other (meth) acrylic acid C _1-18 alkyl esters that can be preferably used include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2EHMA) And isostearyl acrylate (ISTA).

  The constituent monomer component of the acrylic polymer contains, along with the (meth) acrylic acid alkyl ester as the main component, if necessary, another monomer (copolymerizable monomer) copolymerizable with the (meth) acrylic acid alkyl ester It may be. As the copolymerizable monomer, a monomer having a polar group (eg, a carboxy group, a hydroxy group, etc.) can be suitably used. A monomer having a polar group can serve to introduce a crosslinking point into the acrylic polymer or to enhance the cohesion of the acrylic polymer. The copolymerizable monomers can be used alone or in combination of two or more.

As non-limiting specific examples of copolymerizable monomers, the following may be mentioned.
Carboxy group-containing monomers: for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
Hydroxy group-containing monomer: for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) Hydroxyalkyl (meth) acrylates such as acrylates; monomers having a hydroxy group and an amide group such as N- (2-hydroxyethyl) acrylamide (HEAA).
Nitrogen-containing monomers: for example, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinyl-3-morpholinone, N -Vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholindione, N-acryloyl morpholine, N-vinyl carboxylic acid amide and the like.
In addition, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy group-containing monomers, vinyl ether monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, acid anhydride group-containing monomers, etc.

  When such a copolymerizable monomer is used, the amount thereof to be used is not particularly limited, but usually, it is suitable to be 0.01% by weight or more of the total amount of monomer components. The amount of the copolymerizable monomer used may be 0.1% by weight or more, or 1% by weight or more of the total amount of the monomer components, from the viewpoint of exhibiting the effects of the use of the copolymerizable monomer better. The amount of the copolymerizable monomer used can be 50% by weight or less of the total amount of the monomer components, and is preferably 40% by weight or less. Thereby, the cohesive force of the pressure-sensitive adhesive can be prevented from becoming too high, and the tackiness at normal temperature (25 ° C.) can be improved.

  In some embodiments, the acrylic polymer preferably contains, as its constituent monomer component, at least one monomer selected from the group consisting of N-vinyl cyclic amides and hydroxyl group-containing monomers.

  By using N-vinyl cyclic amide, the cohesion and polarity of the pressure-sensitive adhesive are adjusted, and the adhesion after heating as a stimulus to increase the adhesion is improved (hereinafter also referred to as "adhesion after heating"). It can be done. Specific examples of the N-vinyl cyclic amide include those having the corresponding structure among the above-mentioned nitrogen-containing monomers. Particularly preferred examples include N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam. The amount of N-vinyl cyclic amide used is not particularly limited, but generally 0.01% by weight or more (preferably 0.1% by weight or more, for example 0.5% by weight or more) of the total amount of constituent monomer components of the acrylic polymer It is appropriate to In some embodiments, the amount of N-vinyl cyclic amide used may be 1 wt% or more, 5 wt% or more, 8 wt% or more, 10 wt% or more of the total amount of the above monomer components. It may be 12% by weight or more. In addition, from the viewpoint of improving tackiness at normal temperature (25 ° C.) and flexibility at low temperature, the amount of N-vinyl cyclic amide used is usually 40% by weight or less of the total amount of the above monomer components. 30 wt% or less, 25 wt% or less, 20 wt% or less, or 18 wt% or less.

  By using a hydroxyl group-containing monomer, the cohesion and polarity of the pressure-sensitive adhesive can be adjusted to improve the adhesion after heating. In addition, the hydroxyl group-containing monomer can provide a reaction point with a crosslinking agent (for example, an isocyanate-based crosslinking agent) described later, and can enhance the cohesion of the adhesive by the crosslinking reaction. Preferred examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4HBA), and N- (2-hydroxyethyl) acrylamide (HEAA). The amount of the hydroxyl group-containing monomer to be used is not particularly limited, but usually 0.01% by weight or more (preferably 0.1% by weight or more, for example 0.5% by weight or more) of the total constituent monomer components of the acrylic polymer Is appropriate. In some embodiments, the amount of the hydroxyl group-containing monomer used may be 1% by weight or more, 5% by weight or more, or 10% by weight or more of the total amount of the monomer components. In addition, from the viewpoint of improving tackiness at normal temperature (25 ° C.) and improving flexibility at low temperature, the amount of the hydroxyl group-containing monomer used is usually 40% by weight or less of the total amount of the above monomer components. The content may be less than or equal to 20% by weight, or less than or equal to 10% by weight, or less than or equal to 5% by weight.

  In some embodiments, an N-vinyl cyclic amide and a hydroxyl group-containing monomer can be used in combination as the copolymerizable monomer. In this case, the total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer may be, for example, 0.1% by weight or more, 1% by weight or more, or 5% by weight of the total constituent monomer components of the acrylic polymer. The content may be 10% by weight, 15% by weight, 20% by weight or 25% by weight. The total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer can be, for example, 50% by weight or less of the total amount of the above-mentioned monomer components, and preferably 40% by weight or less.

In the embodiment in which the N-vinyl cyclic amide and the hydroxyl group-containing monomer are used in combination, the relationship (by weight) between the amount of _N -vinyl cyclic amide used (W _N ) and the amount of hydroxyl group-containing monomer used (W _OH ) is particularly limited I will not. For example, W _N / W _OH may be 0.01 or more, and usually 0.05 or more is appropriate, 0.1 or more may be 0.2, 0.5 or more may be, or 0 .7 or more may be sufficient. In addition, W _N / W _OH may be, for example, 100 or less, and usually 20 or less is appropriate, may be 10 or less, 5 or less, 2 or less, 1.5 or less, or 1. It may be 3 or less.

  The Tg of polymer A is typically less than 0 ° C., preferably less than −10 ° C., more preferably less than −20 ° C. A pressure-sensitive adhesive containing a polymer A having a Tg of less than 0 ° C. exhibits adequate fluidity (for example, the mobility of polymer chains contained in the pressure-sensitive adhesive), and therefore, the adhesive strength can be obtained by heat treatment at any timing. It is easy to raise In some embodiments, the Tg of polymer A may be, for example, less than -30 ° C, may be less than -40 ° C, may be less than -50 ° C, and may be less than -60 ° C. The lower limit of the Tg of the polymer A is not particularly limited. From the viewpoint of the availability of the material and the improvement of the cohesion of the pressure-sensitive adhesive layer, a polymer A having a Tg of −80 ° C. or more can usually be suitably employed.

In this specification, the Tg of a polymer refers to a nominal value described in the literature, a catalog or the like, or a Tg determined by the Fox equation based on the composition of monomer components used for preparation of the polymer. The Fox equation is, as shown below, a relationship between the Tg of the copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer.
1 / Tg = Σ (Wi / Tgi)
In the above Fox equation, Tg is the glass transition temperature of the copolymer (unit: K), Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio by weight), Tgi is a homopolymer of monomer i Represents the glass transition temperature (unit: K) of When the target polymer of the Tg specification is a homopolymer, the Tg of the homopolymer matches the Tg of the target polymer.

  As a glass transition temperature of the homopolymer used for calculation of Tg, the value as described in a well-known data shall be used. Specifically, numerical values are given in “Polymer Handbook” (Third Edition, John Wiley & Sons, Inc., 1989). The highest value is adopted about the monomer in which a plurality of types of values are described in the above-mentioned Polymer Handbook.

  Although not particularly limited, the weight-average molecular weight (Mw) of the polymer A is usually suitably about 50,000 or more, and from the viewpoint of obtaining a pressure-sensitive adhesive exhibiting better cohesion, for example, 100,000 That may be more than, 200,000 or more, 300,000 or more, 500,000 or more, 700,000 or more. In addition, it is appropriate that Mw of the polymer A is usually about 5,000,000 or less. The polymer A of such Mw is suitable for realizing a pressure-sensitive adhesive sheet having a high adhesion increase ratio, since it is easy to form a pressure-sensitive adhesive that exhibits appropriate fluidity (motility of polymer chains). In some embodiments, the Mw of the polymer A may be 3 million or less, 2 million or less, or 1.5 million or less.

  In this specification, the Mw of the polymer can be determined by gel permeation chromatography (GPC) in terms of polystyrene. More specifically, Mw can be measured according to the method and conditions described in the examples described later.

  The method for obtaining an acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for acrylic polymers, such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization, etc. Can be adopted as appropriate.

  The initiator used for the polymerization can be appropriately selected from conventionally known thermal initiators, photoinitiators and the like according to the polymerization method. Non-limiting examples of thermal initiators include azo initiators such as 2,2'-azobisisobutyronitrile (AIBN), persulfates such as potassium persulfate, peroxide initiators, redox Examples include initiators and the like. Non-limiting examples of photoinitiators include benzoin ether photoinitiators, acetophenone photoinitiators, α-ketol photoinitiators, aromatic sulfonyl chloride photoinitiators, photoactive oxime photoinitiators, Benzoin photoinitiators, benzyl photoinitiators, benzophenone photoinitiators, ketal photoinitiators, thioxanthone photoinitiators, acyl phosphine oxide photoinitiators, etc. may be mentioned. The initiators can be used alone or in combination of two or more.

  In some embodiments, solution polymerization may be preferably employed as a method of obtaining an acrylic polymer. Ethyl acetate, toluene or the like is used as a solvent for solution polymerization. The solution concentration is usually about 20 to 80% by weight. As the initiator, various known ones such as azo type and peroxide type can be used. Chain transfer agents may be used to control molecular weight. The reaction temperature may be usually about 50 to 80 ° C., and the reaction time may be usually about 1 to 8 hours.

  In some embodiments, the acrylic polymer is a partially polymerized product in which a portion of the monomer component is polymerized by irradiating ultraviolet light (UV) to a mixture in which the initiator is blended with the monomer component as described above (acrylic polymer In the form of syrup, it can be included in the pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer. A pressure-sensitive adhesive composition containing such an acrylic polymer syrup can be applied to a predetermined object, and UV irradiation can be performed to complete the polymerization. That is, the said acrylic polymer syrup can be grasped | ascertained as a precursor of an acrylic polymer. The pressure-sensitive adhesive layer (1) can be formed, for example, using a pressure-sensitive adhesive composition containing such an acrylic polymer syrup and the polymer B.

(Siloxane structure-containing polymer B)
The siloxane structure-containing polymer B (hereinafter sometimes abbreviated as “polymer B”) is a copolymer of a monomer having a polyorganosiloxane skeleton (hereinafter also referred to as “monomer S1”) and a (meth) acrylic monomer. It is a polymer. The polymer B can function as a tackiness increase retarder that contributes to the suppression of the initial tackiness and the improvement of the tackiness increase ratio due to the low polarity and motility of the polyorganosiloxane structure derived from the monomer S1. The monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used. Monomer S1 promotes uneven distribution of polymer B on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet before use (before bonding to the adherend) due to the low polarity derived from its structure, and light peeling at the initial stage of bonding Develop sex (low tackiness). As the monomer S1, one having a structure having a polymerizable reactive group at one end can be preferably used. By such copolymerization of the monomer S1 and the (meth) acrylic monomer, a polymer B having a polyorganosiloxane skeleton in the side chain is formed. The polymer B having such a structure tends to have low initial tack and high tack increase ratio due to the mobility and mobility of the side chain.

ここで、上記一般式（１），（２）中のＲ^３は水素またはメチルであり、Ｒ^４はメチル基または１価の有機基であり、ｍおよびｎは０以上の整数である。 As the monomer S1, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, X-22-174ASX, X-22-2426, X-22-2475, KF-2012 etc. are mentioned as one end reactive silicone oil made by Shin-Etsu Chemical Co., Ltd. The monomers S1 can be used alone or in combination of two or more.

Here, R ³ in the above general formulas (1) and (2) is hydrogen or methyl, R ⁴ is a methyl group or a monovalent organic group, and m and n are integers of 0 or more.

  The functional group equivalent of the monomer S1 is, for example, preferably 700 g / mol or more and less than 15000 g / mol, more preferably 800 g / mol or more and less than 10000 g / mol, and preferably 850 g / mol or more and less than 6000 g / mol. Is more preferable, and particularly preferably 1500 g / mol or more and less than 5000 g / mol. When the functional group equivalent of monomer S1 is less than 700 g / mol, the initial tack may not be sufficiently suppressed. When the functional group equivalent of the monomer S1 is 15000 g / mol or more, the increase in adhesion may be insufficient. When the functional group equivalent of monomer S1 is within the above range, the compatibility (for example, compatibility with polymer A) and mobility in the pressure-sensitive adhesive layer can be easily adjusted to an appropriate range, and the initial low tackiness and lamination It becomes easy to implement | achieve the adhesive sheet which makes compatible with the strong adhesiveness at the time of body use by a high level.

Here, "functional group equivalent" means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to one functional group. The title unit g / mol is converted to 1 mol of functional group. The functional group equivalent of monomer S1 can be calculated, for example, from the spectral intensity of ¹ H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). Calculating functional group equivalent of the monomer S1, based on the spectral intensity of ^{1 H-NMR (g / mol} ) ^is, 1 H-NMR based on general structure analysis method according to the spectral analysis, Japanese Patent No. 5951153, if necessary It can carry out with reference to the description of the publication.

When two or more kinds of monomers having different functional group equivalents are used as the monomer S1, an arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of monomer S1 consisting of n types of monomers (monomer S1 ₁ , monomer S1 ₂ ... Monomer S1 _n ) having different functional group equivalents can be calculated by the following formula.
Functional group equivalent of the monomer S1 (g / mol) = (monomer S1 ₁ functional group equivalent × monomer S1 ₁ of the amount + monomer S1 ₂ functional group equivalent × monomer S1 ₂ of the amount + ... + monomer S1 _n of the amount of the functional group equivalent × monomer S1 _n) / (monomer S1 ₁ of the amount + monomer S1 ₂ of the amount + ... + amount of monomer S1 _n)

  The content of the monomer S1 may be, for example, 5% by weight or more with respect to all the monomer components for preparing the polymer B, and 10% by weight or more from the viewpoint of exhibiting the effect as an adhesive force increase retarder better It is preferable to set it as 15 weight% or more, and it is good also as 20 weight% or more. In addition, the content of the monomer S1 is suitably 60% by weight or less with respect to all the monomer components for preparing the polymer B from the viewpoint of polymerization reactivity and compatibility, and 50% by weight or less It may be 40% by weight or less, or 30% by weight or less. If the content of the monomer S1 is less than 5% by weight, the initial tack may not be sufficiently suppressed. When the content of the monomer S1 is more than 60% by weight, the increase in adhesion may be insufficient.

  The monomer component used for the preparation of the polymer B contains, in addition to the monomer S1, (meth) acrylic monomers copolymerizable with the monomer S1. The mobility of the polymer B in the pressure-sensitive adhesive layer can be suitably controlled by copolymerizing one or more kinds of (meth) acrylic monomers with the monomer S1. Copolymerizing the monomer S1 and the (meth) acrylic monomer may also help to improve the compatibility of the polymer B with the polymer A (for example, an acrylic polymer).

As a (meth) acrylic-type monomer, the (meth) acrylic-acid alkylester is mentioned, for example. For example, one or more of the monomers exemplified above as (meth) acrylic acid alkyl esters that can be used when the polymer A is an acrylic polymer can be used as a copolymerization component of the polymer B. In some embodiments, polymer B is a (meth) acrylic acid C _4-12 alkyl ester (preferably a (meth) acrylic acid C _4-10 alkyl ester, such as a (meth) acrylic acid C _6-10 alkyl ester) At least one may be contained as a monomer unit. In some other embodiments, the polymer B contains at least one of methacrylic acid C _1-18 alkyl ester (preferably methacrylic acid C _1-14 alkyl ester, for example methacrylic acid C _1-10 alkyl ester) as a monomer unit It can. The monomer units constituting the polymer B may include, for example, one or more selected from MMA, BMA and 2EHMA.

  Another example of the (meth) acrylic monomer is a (meth) acrylic acid ester having an alicyclic hydrocarbon group. For example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate and the like can be used. In some embodiments, the polymer B may contain at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate as monomer units.

  The amount of the (meth) acrylic acid alkyl ester and the alicyclic hydrocarbon group-containing (meth) acrylic acid ester used is, for example, 10% by weight or more and 95% by weight with respect to all the monomer components for preparing the polymer B % May be 20% to 95% by weight, may be 30% to 90% by weight, 40% to 90% by weight, or 50% to 85% by weight.

  As another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the polymer B, various copolymerizable monomers exemplified above as the monomers that can be used when the polymer A is an acrylic polymer can be mentioned.

  In some embodiments, by including also in the polymer A a monomer unit common to the monomer unit contained in the polymer B, the mobility of the polymer B in the pressure-sensitive adhesive layer can be improved, and the adhesion increase ratio can be improved. . It is effective that the common monomer unit is a component that occupies 5% by weight or more of the total monomer units constituting the polymer B, 10% by weight or more (more preferably 20% by weight or more, for example 30% by weight or more) It is preferable that it is an ingredient which occupies. The ratio of the common monomer unit to the total monomer units constituting the polymer A may be, for example, 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and 7% by weight or more It may be When the ratio of the common monomer units to the total monomer units constituting the polymer A is high, the effect of improving the compatibility tends to be exhibited better. Also, in consideration of the balance with other properties, the ratio of the common monomer unit to the total monomer units constituting the polymer A may be 50% by weight or less, 30% by weight or less, or 15% by weight or less Good. Non-limiting examples of monomers that can be preferably employed as common monomer units, MMA, BMA, 2EHMA, methyl acrylate (MA), BA, 2 EHA, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl Examples include (meth) acrylates and the like.

  The Mw of the polymer B is not particularly limited. The Mw of the polymer B may be, for example, 1,000 or more, or 5,000 or more. From the viewpoint of enhancing the adhesion increase by heating, in some embodiments, the Mw of the polymer B may be, for example, 10000 or more, 12000 or more, 15000 or more, 17000 or more, 20000 or more . In addition, the Mw of the polymer B may be, for example, 500000 or less, and may be 350,000 or less. From the viewpoint of facilitating peeling of the second region from the adherend in the partial removal step, in some embodiments, the Mw of the polymer B may be, for example, 100000 or less, 70000 or less, or 50000 or less. It may be less than 50,000, less than 40,000, less than 35,000, less than 30,000, less than 28,000, or less than 25,000. When the Mw of the polymer B is within the range of any of the upper limit and the lower limit described above, the compatibility and mobility in the pressure-sensitive adhesive layer can be easily adjusted to an appropriate range, and the low tackiness in the partial removal step It becomes easy to be compatible in the high level with the strong adhesiveness at the time of laminated body use.

  The polymer B can be produced, for example, by polymerizing the above-described monomer by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization and the like.

  A chain transfer agent can be used to adjust the molecular weight of polymer B. Examples of chain transfer agents used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, α-thioglycerol, etc .; thioglycolic acid; methyl thioglycollate Ethyl thioglycollate, propyl thioglycollate, butyl thioglycollate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycollate, dodecyl thioglycolate, Thioglycolic acid esters such as thioglycolic acid ester of ethylene glycol, thioglycolic acid ester of neopentyl glycol, thioglycolic acid ester of pentaerythritol; α- Methyl styrene dimer; and the like.

  The amount of chain transfer agent used is not particularly limited, but generally 0.05 parts by weight to 20 parts by weight, preferably 0.1 parts by weight to 15 parts by weight, and more preferably 0 parts by weight per 100 parts by weight of the monomer. .2 parts by weight to 10 parts by weight is appropriate. By adjusting the amount of chain transfer agent used in this manner, polymer B having a suitable molecular weight can be obtained. The chain transfer agent can be used alone or in combination of two or more.

  Although not particularly limited, the use amount of the polymer B can be, for example, 0.1 parts by weight or more with respect to 100 parts by weight of the polymer A, and from the viewpoint of obtaining higher effects, 0.3 It may be at least one part by weight, may be at least 0.4 parts by weight, may be at least 0.5 parts by weight, and may be at least 1 part by weight or at least 2 parts by weight. In addition, the amount of polymer B used may be, for example, 75 parts by weight or less, 50 parts by weight or less, or 20 parts by weight or less, from the viewpoint of avoiding an excessive decrease in cohesive force. It may be at most 8 parts by weight, or at most 5 parts by weight.

  The pressure-sensitive adhesive layer may optionally contain a polymer (optional polymer) other than the polymer A and the polymer B, as long as the effects obtained by the technology disclosed herein are not significantly impaired. An appropriate amount of such an optional polymer is usually 20% by weight or less of the entire polymer component contained in the pressure-sensitive adhesive layer. In some embodiments, the amount of the optional polymer used may be 5% by weight or less, or 1% by weight or less of the entire polymer component. The pressure-sensitive adhesive layer may contain substantially no polymer other than the polymer A and the polymer B.

(Crosslinking agent)
In the pressure-sensitive adhesive layer, a crosslinking agent may be used as needed for the purpose of adjusting the cohesion force and the like. As the crosslinking agent, crosslinking agents known in the field of pressure-sensitive adhesives can be used. For example, isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, carbodiimide crosslinking agents, metal chelates The crosslinking agent etc. can be mentioned. In particular, isocyanate crosslinking agents, epoxy crosslinking agents, and metal chelate crosslinking agents are preferable. The crosslinking agents can be used singly or in combination of two or more. The art disclosed herein can be preferably practiced in the aspect of using at least an isocyanate-based crosslinking agent as the crosslinking agent.

  Examples of isocyanate crosslinking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate Isocyanate, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (eg, Toronso "Coronate L"), trimethylolpropane / hexamethylene Diisocyanate trimer adducts (for example, "Coronate HL" manufactured by Tosoh Corp.), trimethylolpropane adducts of xylylene diisocyanate (for example, Sulfonates D110N ", isocyanurate of hexamethylene diisocyanate (e.g., manufactured by Tosoh" Coronate HX ") isocyanate adducts of the like.

  Examples of epoxy crosslinking agents include bisphenol A, epoxy resins of epichlorohydrin type, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triol. Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ', N'-tetraglycidyl-m-xylylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane etc. Can.

  The amount used in the case of using the crosslinking agent is not particularly limited. In some embodiments, the use amount of the crosslinking agent relative to 100 parts by weight of the polymer A may be, for example, 0.01 parts by weight or more, may be 0.05 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight It may be 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more. By increasing the amount of crosslinking agent used, higher cohesion tends to be obtained. On the other hand, from the viewpoint of avoiding a decrease in tack due to excessive cohesion, the amount of the crosslinking agent used per 100 parts by weight of the polymer A is usually 15 parts by weight or less, and may be 10 parts by weight or less. It may be 5 parts by weight or less. If the amount of the crosslinking agent used is not too large, it may be advantageous from the viewpoint of making the use effect of the polymer B better by utilizing the fluidity of the pressure-sensitive adhesive.

  A crosslinking catalyst may be used to promote the crosslinking reaction more effectively. Examples of the crosslinking catalyst include metal-based crosslinking catalysts such as tetra-n-butyltitanate, tetraisopropyltitanate, ferric nasem, butyltin oxide, and dioctyltin dilaurate. Among them, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferable. The use amount of the crosslinking catalyst is not particularly limited, and can be, for example, about 0.0001 parts by weight to 1 part by weight (typically 0.05 parts by weight or less) with respect to 100 parts by weight of the polymer A.

A polyfunctional monomer can be used for the adhesive layer as needed. Multifunctional monomers can serve for purposes such as adjustment of cohesion by being used in place of or in combination with the above-mentioned crosslinking agents. For example, in the pressure-sensitive adhesive layer formed from a photocurable pressure-sensitive adhesive composition, a polyfunctional monomer can be preferably used.
Examples of multifunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecane Diol di (meth) acrylate, trimethylol propane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, allyl (meth) acrylate, bi Le (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl diol (meth) acrylate, hexyl di (meth) acrylate. Among them, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be suitably used. The polyfunctional monomers can be used alone or in combination of two or more.

  The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but normally, it is appropriate to be in the range of about 0.01 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the polymer A . In some embodiments, the amount of multifunctional monomer used may be, for example, 0.02 parts by weight or more, or 0.03 parts by weight or more, with respect to 100 parts by weight of the polymer A. By increasing the amount of multifunctional monomer used, higher cohesion tends to be obtained. On the other hand, the amount of the polyfunctional monomer used may be 2.0 parts by weight or less, and even 1.0 part by weight or less with respect to 100 parts by weight of the polymer A, from the viewpoint of avoiding a decrease in tack due to excessive cohesion. It may well be 0.5 parts by weight or less. Not using too much amount of the polyfunctional monomer may be advantageous also from the viewpoint of making the use effect of the polymer B better by utilizing the fluidity of the adhesive.

(Tackifying resin)
The pressure-sensitive adhesive layer can optionally contain a tackifying resin. The tackifier resin is not particularly limited, and, for example, rosin-based tackifier resin, terpene-based tackifier resin, phenol-based tackifier resin, hydrocarbon-based tackifier resin, ketone-based tackifier resin, polyamide-based tackifier resin, Epoxy tackifying resins, elastomeric tackifying resins and the like can be mentioned. The tackifying resin can be used singly or in combination of two or more.

  In the embodiment in which the tackifier resin is contained in the pressure-sensitive adhesive layer, the content of the tackifier resin is not particularly limited, and can be set so as to exhibit appropriate adhesion performance depending on the purpose and application. The content of the tackifier resin (the total amount of two or more tackifier resins, if any, of the two or more tackifier resins) relative to 100 parts by weight of the polymer A can be, for example, about 5 to 500 parts by weight. In the technique disclosed herein, the content of the tackifier resin relative to 100 parts by weight of the polymer A is less than 5 parts by weight, less than 2 parts by weight or less than 1 part by weight, or the pressure-sensitive adhesive layer is substantially tackified The embodiment which does not contain a resin can be preferably practiced.

  As the tackifying resin, those having a softening point (softening temperature) of about 80 ° C. or more (preferably, about 100 ° C. or more, for example, about 120 ° C. or more) can be preferably used. With a tackifying resin having a softening point above the lower limit value described above, the initial low tackiness and the strong tackiness when using a laminate tend to be effectively improved. The upper limit of the softening point is not particularly limited, and may be, for example, about 200 ° C. or less (typically, 180 ° C. or less). The softening point of the tackifying resin can be measured based on the softening point test method (ring and ball method) defined in JIS K2207.

(Formation of adhesive layer)
The pressure-sensitive adhesive layer (1) may be a cured layer of a pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive layer (1) can be formed by appropriately applying a water-dispersed, solvent-type, light-curable, or hot-melt type pressure-sensitive adhesive composition to a suitable surface and then curing treatment. . When two or more curing treatments (drying, crosslinking, polymerization, cooling, etc.) are carried out, these can be carried out simultaneously or in multiple stages. In a pressure-sensitive adhesive composition using a partially polymerized product of monomer components (acrylic polymer syrup), a final copolymerization reaction is typically performed as the above-mentioned curing treatment. That is, the partially polymerized product is subjected to a further copolymerization reaction to form a completely polymerized product. For example, if it is a photocurable pressure-sensitive adhesive composition, light irradiation is carried out. If necessary, curing treatment such as crosslinking or drying may be performed. For example, when it is necessary to dry with a photocurable pressure-sensitive adhesive composition, light curing may be performed after drying. In the case of a pressure-sensitive adhesive composition using a completely polymerized product, typically, a treatment such as drying (heat drying) or crosslinking is carried out as the curing treatment as necessary.

  The application of the pressure-sensitive adhesive composition can be carried out using, for example, a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater. The application of the pressure-sensitive adhesive composition and the other pressure-sensitive adhesive composition used to form the pressure-sensitive adhesive layer (2) described later can be carried out in the same manner.

<Pressure-sensitive adhesive layer formed of a photocurable composition containing a base polymer P and a photocuring agent>
The pressure-sensitive adhesive layer (2) contains a base polymer P and a light curing agent, and shows a property of being cured by irradiation with an actinic ray (eg, UV) to improve adhesion. By utilizing such properties, for example, the adhesive force before photo-curing is configured to be 2 N / 25 mm or less, the sticking step, the cutting step and the partial removing step are carried out before the photo curing, In the aspect of raising the force (typically, raising it to 5 N / 25 mm or more), it can be suitably used to practice the laminate manufacturing method disclosed herein. It is preferable that the adhesive composition (photocurable composition) which comprises an adhesive layer (2) contains a photoinitiator from a viewpoint of raising the efficiency of hardening by actinic radiation irradiation. From the viewpoint of suppressing the phenomenon that the adhesive remains on the adherend when the adhesive sheet in the second region is peeled and removed in the partial removal step by hardening the adhesive layer before light curing, that is, the adhesive residue phenomenon Preferably, a cross-linked structure is introduced to the base polymer P.

(Base polymer P)
An acrylic polymer can be preferably used as the base polymer P (hereinafter sometimes abbreviated as “polymer P”) of the pressure-sensitive adhesive layer (2) from the viewpoint of optical transparency and the like. For example, it is preferable that 50% by weight or more of the pressure-sensitive adhesive layer (2) is an acrylic polymer. As the acrylic polymer, one in which 40% by weight or more of the total amount of constituent monomer components is the same (meth) acrylic acid alkyl ester as the above-mentioned polymer A can be preferably used.

  The acrylic polymer preferably contains, as a copolymerization component, a monomer component having a crosslinkable functional group. Examples of the monomer having a crosslinkable functional group include a hydroxy group-containing monomer and a carboxy group-containing monomer. As an example of a hydroxy-group containing monomer and a carboxy-group containing monomer, the thing similar to the monomer illustrated as a constituent monomer component of the polymer A contained in an adhesive layer (1) is mentioned. Among them, it is preferable to contain a hydroxy group-containing monomer. The hydroxy group and the carboxy group of the polymer P become reaction points with the crosslinking agent described later. By introducing a crosslinked structure into the polymer P, the cohesion is improved, the adhesion of the pressure-sensitive adhesive layer (2) is improved, and the flowability of the pressure-sensitive adhesive is decreased. Adhesive residue tends to be reduced.

  The total content of the hydroxy group-containing monomer and the carboxy group-containing monomer is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, with respect to the total amount of constituent monomer components of the acrylic polymer. More preferably, it is in weight percent. In particular, the content of the (meth) acrylic acid ester containing a hydroxy group is preferably in the above range.

  The acrylic polymer preferably contains a nitrogen-containing monomer as a constituent monomer component. As an example of a nitrogen-containing monomer, the thing similar to the monomer illustrated as a constituent monomer component of the polymer A contained in an adhesive layer (1) is mentioned. The content of the nitrogen-containing monomer with respect to the total amount of constituent monomer components is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and still more preferably 5 to 20% by weight. The acrylic polymer preferably contains N-vinylpyrrolidone in the above range as the nitrogen-containing monomer.

  When the acrylic polymer contains both a hydroxy group-containing monomer and a nitrogen-containing monomer as monomer components, the cohesion and transparency of the pressure-sensitive adhesive tend to be enhanced. The total content of the hydroxy group-containing monomer and the nitrogen-containing monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and more preferably 15 to 35% by weight based on the total amount of constituent monomer components. It is further preferred that

  Acrylic polymers include monomer components other than those described above, such as cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy group-containing monomers, vinyl ether monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, acid anhydride groups You may contain the containing monomer etc.

  In the acrylic polymer, the content of a monomer having a homopolymer Tg of 40 ° C. or more is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of constituent monomer components of the acrylic polymer. Is more preferred. From the viewpoint of suppressing adhesive residue in the partial removal step, the constituent monomer component of the polymer P preferably contains a monomer component having a homopolymer Tg of 80 ° C. or more, and a homopolymer monomer having a Tg of 100 ° C. or more It is more preferable to include. In the acrylic polymer, the content of a monomer having a homopolymer Tg of 100 ° C. or more based on the total amount of constituent monomer components is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, It is more preferably 1% by weight or more, and particularly preferably 3% by weight or more. In particular, the content of MMA is preferably in the above range. The preferred range of the Tg of the acrylic polymer used as the polymer P may be the same as the preferred Tg of the polymer A described above.

  The acrylic polymer can be obtained by various known polymerization methods as the polymer A contained in the pressure-sensitive adhesive layer (1). For example, solution polymerization may be preferably employed.

  The adhesion of the pressure-sensitive adhesive layer before light curing tends to depend on the constituent components and the molecular weight of the polymer P. The weight average molecular weight of the acrylic polymer is preferably 100,000 to 5,000,000, more preferably 300,000 to 3,000,000, and more preferably 500,000, from the viewpoint of achieving both adequate adhesiveness and suppression of adhesive residue in the partial removal step. -2,000,000 is more preferable. In addition, when a crosslinked structure is introduce | transduced into the polymer P, the molecular weight of the polymer P points out the molecular weight before crosslinked structure introduction.

(Crosslinking agent)
From the viewpoint of imparting an appropriate cohesive force to the pressure-sensitive adhesive, it is preferable that a crosslinked structure is introduced to the polymer P. For example, a crosslinking agent is added to the solution after polymerizing the polymer P, and if necessary, heating is performed to introduce a crosslinked structure. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent, a carbodiimide type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned. These crosslinking agents react with functional groups such as hydroxy groups introduced into the polymer P to form a crosslinked structure. As an isocyanate type crosslinking agent, the thing similar to an adhesive layer (1) can be used.

  The amount of the crosslinking agent used may be appropriately adjusted according to the composition, molecular weight and the like of the polymer P. The amount of the crosslinking agent used may be, for example, about 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the polymer P. More preferably, it is 1 to 4 parts by weight. A crosslinking catalyst may be used in the same manner as in the pressure-sensitive adhesive layer (1) in order to accelerate the formation of a crosslinked structure.

(Photo-curing agent)
The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer (2) is configured to exhibit photocurability by containing a light curing agent in addition to the polymer P. The pressure-sensitive adhesive layer (2) exhibits the property of being cured by light and improving the adhesion by irradiation with an actinic ray as a stimulus for increasing the adhesion after bonding to the adherend.

  As a photocuring agent, a photocurable monomer or a photocurable oligomer is used. As a light curing agent, a compound having two or more ethylenic unsaturated bonds in one molecule is preferable. The photo-curing agent is preferably a compound showing compatibility with the polymer P. The photo-curing agent is preferably one that is liquid at normal temperature, since it exhibits appropriate compatibility with the polymer P. By the photo-curing agent being compatible with the polymer P and uniformly dispersed in the composition, the contact area with the adherend can be secured, and a highly transparent pressure-sensitive adhesive layer (2) can be formed.

  The compatibility of the polymer P with the light curing agent is mainly influenced by the structure of the compound. The structure and compatibility of the compound can be evaluated, for example, by the Hansen solubility parameter, and the smaller the difference between the solubility parameters of the polymer P and the light curing agent, the higher the compatibility tends to be.

  It is preferable to use a polyfunctional (meth) acrylate as the light curing agent because of high compatibility with the acrylic polymer. As polyfunctional (meth) acrylates, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide Modified di (meth) acrylate, alkanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol La (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate And urethane (meth) acrylate, epoxy (meth) acrylate, butadiene (meth) acrylate, isoprene (meth) acrylate and the like.

  The compatibility of the polymer P with the light curing agent also depends on the molecular weight of the compound. The smaller the molecular weight of the photocurable compound, the higher the compatibility with the polymer P tends to be. From the viewpoint of compatibility with the polymer P, the molecular weight of the light curing agent is preferably 1,500 or less, and more preferably 1,000 or less.

  The type and content of the light curing agent mainly affect the adhesion after light curing. As the functional group equivalent is smaller (that is, the number of functional groups per unit molecular weight is larger) and the content of the photo-curing agent is larger, the adhesion after photo-curing tends to be larger.

  From a viewpoint of raising the adhesive force after photocuring, 500 or less are preferable and, as for the functional group equivalent (g / eq) of a photocuring agent, 450 or less are more preferable. On the other hand, when the photocrosslinking density is excessively increased, the viscosity of the pressure-sensitive adhesive may be reduced to lower the adhesion. Therefore, the functional group equivalent of the photo-curing agent is preferably 100 or more, more preferably 130 or more, still more preferably 150 or more, and particularly preferably 180 or more.

  In the combination of the acrylic polymer and the polyfunctional acrylate photo-curing agent, when the functional group equivalent of the photo-curing agent is small, the interaction between the polymer P and the photo-curing agent is strong, and the adhesion before photo-curing tends to be high. is there. In the technique disclosed herein, the functional group equivalent of the photocuring agent is within the above range also from the viewpoint of suppressing the adhesion before photocuring to an appropriate range and enhancing the removability of the second region in the partial removal step. Is preferred.

  The content of the photo-curing agent in the pressure-sensitive adhesive composition is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 10 to 35 parts by weight with respect to 100 parts by weight of the polymer P. A photocurable pressure-sensitive adhesive layer is obtained by containing the photocurable compound as an uncured (unreacted) monomer or oligomer in the pressure-sensitive adhesive composition. In order to include the photo-curing agent in the composition in the uncured state, it is preferable to add the photo-curing agent to the polymer solution after polymerizing the polymer P.

  When the content of the photo-curing agent in the pressure-sensitive adhesive composition is increased, the photo-curing agent tends to bleed out on the surface of the pressure-sensitive adhesive layer. When the photocuring agent bleeds out in a large amount, the photocuring agent tends to remain on the adherend after removing the second region. On the other hand, the adhesive force of the pressure-sensitive adhesive layer to the adherend is suppressed by bleeding out a small amount of the photo-curing agent to the surface, and the low adhesiveness before photo curing and the strong adhesiveness after photo curing are both suitably achieved. It is possible to

(Photoinitiator)
The pressure-sensitive adhesive layer (2) preferably contains a photoinitiator. The photoinitiator generates an active species upon irradiation with actinic radiation to accelerate the curing reaction of the photocuring agent. As a photoinitiator, a photo cation initiator (photo acid generator), a photo radical initiator, a photo anion initiator (photo base generator) etc. are used according to the kind etc. of a photo-curing agent. When a polyfunctional acrylate is used as the light curing agent, it is preferable to use a photo radical initiator. Examples of photo radical initiators include hydroxy ketones, benzyl dimethyl ketals, amino ketones, acyl phosphine oxides, benzophenones, trichloromethyl group-containing triazine derivatives, and the like. The photoradical generators may be used alone or in combination of two or more. The content of the photoinitiator in the pressure-sensitive adhesive layer is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the pressure-sensitive adhesive layer.

(Other additives)
In addition to the above components, the pressure-sensitive adhesive layer may be a silane coupling agent, a tackifier, a plasticizer, a softener, an antidegradant, a filler, a colorant, an ultraviolet absorber, an antioxidant, and a surfactant. An additive such as an antistatic agent may be contained within a range that does not significantly impair the effects obtained by the technology disclosed herein.

(Formation of adhesive layer)
The pressure-sensitive adhesive layer (2) is, for example, applied to a suitable surface of a pressure-sensitive adhesive composition containing polymer P, a photo-curing agent and other components which are optionally used, and then the solvent is optionally removed by drying. It can be formed by As a drying method, a suitable method may be adopted suitably. The heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and further preferably 70 ° C to 170 ° C. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, still more preferably 10 seconds to 10 minutes.

  When the pressure-sensitive adhesive composition contains a crosslinking agent, it is preferable to proceed the crosslinking by heating or aging simultaneously with or after the drying of the solvent. The heating temperature and the heating time are appropriately set depending on the type of the crosslinking agent to be used, and usually, crosslinking is carried out by heating in a range of 20 ° C. to 160 ° C. for about 1 minute to about 7 days. The heating for drying and removing the solvent may be combined with the heating for crosslinking. The photocuring agent remains unreacted even after the crosslinking structure is introduced into the polymer by the crosslinking agent. Therefore, the photocurable pressure-sensitive adhesive layer (2) is formed, which contains the polymer P in which the crosslinked structure is introduced and the unreacted light curing agent.

(Frictional force)
The pressure-sensitive adhesive layer (2) before light curing is a friction force at a frequency of 5 Hz measured by the tapping mode of the friction force microscope (FFM) from the viewpoint of facilitating suppression of the adhesive force. It is preferably 2 to 5 times the force. In addition, when the ratio of the friction force at a frequency of 0.1 Hz to 5 Hz of the pressure-sensitive adhesive layer (2) is in the above range, the adhesion after photocuring tends to be greatly increased compared to before photocuring.

  In the FFM, the force acting between the probe of the scanning probe microscope (SPM) and the sample surface is converted to the displacement (torque amount) of the plate spring of the cantilever, and this displacement is detected electrically. The amount of displacement is proportional to the differential voltage, and the frictional force is proportional to the spring constant and the amount of displacement of the cantilever. Thus, the frictional force is proportional to the FFM differential voltage. The ratio of the friction force at a frequency of 5 Hz to the friction force at a frequency of 0.1 Hz is equal to the ratio of the two FFM difference signals.

  The frictional force by nanotribology tends to reflect the adhesion of the surface of the pressure-sensitive adhesive layer to the adherend, and the small frictional force means that the surface of the pressure-sensitive adhesive is close to liquid and the viscosity is small. . When the surface of the pressure-sensitive adhesive layer has viscosity, the frictional force is increased, and the frictional force measured by the FFM has frequency dependency. The frictional force measured at a specific frequency tends to reflect the individual physical properties of the components of the pressure-sensitive adhesive composition, whereas the frequency dependence tends to more accurately reflect the surface properties. The smaller the frequency dependency of the frictional force, the smaller the viscosity and the stronger the liquid property. The larger the frequency dependency of the frictional force, the larger the viscosity and the higher the adhesion to the adherend tends to be. For example, when the base polymer of the pressure-sensitive adhesive layer and the photo-curing agent are not completely compatible, the liquid photo-curing agent bleeds out to the surface to form an adhesion-inhibiting layer (Weak Boundary Layer) on the adhesive interface with the adherend. WBL) is formed, and the liquid property is enhanced, so that the frequency dependence of the friction force and the friction force tends to be reduced.

  By controlling the compatibility between the polymer P and the photo-curing agent in the pressure-sensitive adhesive layer (2), a small amount of the photo-curing agent may bleed out on the surface of the pressure-sensitive adhesive layer to form WBL. When WBL is properly formed, the characteristics of the surface (adhesion interface) change, and the frequency dependence of the frictional force and the frictional force decreases. As a result, the adhesion before photocuring can be easily suppressed, and the peeling of the second region in the case of performing the partial removal step before the photocuring becomes easy.

  Peeling between the pressure-sensitive adhesive layer and the adherend before light curing becomes easy when the friction force at a frequency of 5 Hz of the pressure-sensitive adhesive layer before light curing is five times or less than the friction force at a frequency of 0.1 Hz. Tend. The friction force at a frequency of 5 Hz of the pressure-sensitive adhesive layer is preferably twice or more, more preferably three times or more, and 3.5 times or more from the viewpoint of avoiding bleeding out of the light curing agent. Is more preferred.

  From the viewpoint of achieving both adequate adhesion to the adherend and releasability, the FFM differential signal at a frequency of 5 Hz of the pressure-sensitive adhesive layer before photocuring measured using a cantilever with a spring constant of 40 N / m is 0.01 -1V is preferable, 0.05-0.9V is more preferable, 0.1-0.8V is more preferable, 0.2-0.7V is especially preferable.

  From the viewpoint of enhancing the adhesion after photocuring, the pressure-sensitive adhesive layer after photocuring preferably has a frictional force at a frequency of 5 Hz measured by FFM at least 5 times the frictional force at a frequency of 0.1 Hz And 5.5 times or more is more preferable. 0.1 V or more is preferable, 0.2 V or more is more preferable, and 0.3 V or more of the FFM differential signal at a frequency of 5 Hz of the pressure-sensitive adhesive layer after photocuring measured using a cantilever with a spring constant of 40 N / m preferable. From the viewpoint of adhesive strength improvement, the larger the frictional force of the pressure-sensitive adhesive layer after photocuring, the better. Therefore, although the upper limit of the frictional force is not particularly limited, the FFM differential signal at 5 Hz measured using a cantilever with a spring constant of 40 N / m is generally 10 V or less, and 5 V or less in consideration of the balance of the adhesive characteristics. Is preferred.

  The friction force at a frequency of 5 Hz of the pressure-sensitive adhesive layer after light curing is preferably 1.5 times or more of the friction force at a frequency of 5 Hz of the pressure-sensitive adhesive layer before light curing, and more preferably twice or more. The above is more preferable, and 3 times or more is particularly preferable. As the ratio of the frictional force before and after the light curing is larger, the increasing rate of the adhesion due to the light curing tends to be higher. The frictional force after photocuring is generally 20 times or less, preferably 10 times or less, of the frictional force before photocuring.

The friction force at a frequency of 0.1 Hz and 5 Hz of the pressure-sensitive adhesive layer before and after photocuring is the FFM mode of a scanning probe microscope ("AFM5300E" manufactured by Hitachi High-Tech Science) under the following conditions. Measurement is performed by performing a fractional measurement with a scan width of 5 μm in the direction (10 μm scan in a reciprocating manner) and reading a differential voltage at a position 3 μm from the left side of the measurement range.
(Measurement condition)
Cantilever: BudgetSensors "Tap 300 E-G" (spring constant 40 N / m equivalent)
ADD value: 8.44V, DIF value: 0.4V, FFM value: 0V
Atmosphere: vacuum, room temperature Scanning rate: 0.1 Hz, 1 Hz and 5 Hz

  As an example of the actinic light which can be utilized for the photocuring of an adhesive layer (2), an ultraviolet-ray (UV), visible light, infrared rays, an X ray, an alpha ray, a beta ray, a gamma ray, etc. are mentioned. UV is preferable as the actinic ray, since curing of the pressure-sensitive adhesive layer in the storage state is easily suppressed and curing is easy. The irradiation intensity and irradiation time of the actinic ray may be appropriately set according to the composition, thickness and the like of the pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive layer (2) is photocurable, and the timing at which the adhesive strength is raised by curing can be arbitrarily set. Therefore, after the adhesive sheet is attached to the adherend, the partial removal process can be performed at an arbitrary timing between the photocuring of the adhesive, so that the lead time of the device manufacturing process can be flexibly coped with. It is.

<Structure of adhesive sheet>
The thickness of the adhesive sheet used for the manufacturing method disclosed here is not specifically limited, For example, 3 micrometers-about 11 mm may be sufficient. From the viewpoint of handleability and the like of the pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive sheet is usually 5 μm or more, preferably 10 μm or more, and may be 30 μm or more. From the viewpoint of peeling workability of the second region in the partial removal step, in some embodiments, a pressure-sensitive adhesive sheet having a thickness of 50 μm or more, 70 μm or more, or 90 μm or more may be preferably used. The adhesive sheet may have a thickness of, for example, 1000 μm or less, 600 μm or less, or 350 μm, from the viewpoint of cutting processability in the cutting step and peeling workability of the second region in the partial removing step. The following may be sufficient, 200 micrometers or less may be sufficient, and 150 micrometers or less may be sufficient.

  In the pressure-sensitive adhesive sheet including the base material layer and the pressure-sensitive adhesive layer, the thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be, for example, in the range of about 1 μm to 1000 μm. In some embodiments, the thickness of the pressure-sensitive adhesive layer may be, for example, 3 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 13 μm or more, 20 μm or more, or 20 μm or more. By increasing the thickness of the pressure-sensitive adhesive layer, a laminate in which the adhesive pieces are more firmly bonded to the adherend tends to be obtained. On the other hand, if the thickness of the pressure-sensitive adhesive layer is excessively large, the workability in the partial removal step may be caused by blocking between the pressure-sensitive adhesive in the first region and the pressure-sensitive adhesive in the second region (for example, first region and second region) And separability) may tend to decrease. From this point of view, the thickness of the pressure-sensitive adhesive layer may be, for example, 300 μm or less, 200 μm or less, 150 μm or less, 100 μm or less, 70 μm or less, 50 μm or less, or 40 μm or less, It may be 30 μm or less.

  In the pressure-sensitive adhesive sheet including the base material layer and the pressure-sensitive adhesive layer, the thickness of the base material layer is not particularly limited, and may be, for example, about 2 μm to 10 mm. In some embodiments, the thickness of the substrate layer may be, for example, 5 μm or more, 10 μm or more, or 25 μm, in some embodiments, from the viewpoint of handling of the adhesive sheet and prevention of breakage of the second region in the partial removal step. More than, 35 micrometers or more may be sufficient, 50 micrometers or more may be sufficient, 60 micrometers or more may be sufficient. In addition, the thickness of the base material layer may be, for example, 1000 μm or less, 500 μm or less, 300 μm or less, or 200 μm or less in some embodiments from the viewpoint of cutting processability in the cutting step, etc. It may be 150 μm or less, 100 μm or less, or 90 μm or less.

  The pressure-sensitive adhesive sheet used in the manufacturing method disclosed herein can be suitably practiced in a mode in which the thickness Ts of the substrate layer is larger than the thickness Ta of the pressure-sensitive adhesive layer. That is, it is preferable that Ts / Ta be greater than one. Although not particularly limited, Ts / Ta may be, for example, 1.1 or more, 1.2 or more, 1.5 or more, 2 or more, or 2.5 or more. Further, Ts / Ta may be, for example, 50 or less, 20 or less, 10 or less, or 7 or less. Favorable peeling workability in the partial removal step and lamination finally obtained by using a pressure-sensitive adhesive sheet having a configuration satisfying any of the upper limit described above and / or any of the lower limit described above The firm adhesion of the adhesive piece to the adherend in the body tends to be balanced and balanced.

In some embodiments, the pressure-sensitive adhesive sheet used in the attaching step may have, for example, an area of 2500 cm ² or more and a short side of 50 cm or more. Thus, in the aspect using a large-sized adhesive sheet, it is particularly significant to adopt the manufacturing method disclosed herein. By using such a pressure-sensitive adhesive sheet, one or more effects tend to be suitably exhibited among, for example, the improvement of positional accuracy, the improvement of shape accuracy, and the improvement of productivity. Further, according to the manufacturing method disclosed herein, the partial removal step of peeling and removing the second region of the pressure-sensitive adhesive sheet is performed before the adhesion of the pressure-sensitive adhesive sheet to the adherend exceeds 2 N / 25 mm. Even if it is a large-sized adhesive sheet, it is easy to carry out peeling removal of the second region. According to the embodiment in which the area of the pressure-sensitive adhesive sheet is 3600 cm ² or more, more preferably 4900 cm ² or more, or the embodiment in which the short side length is 60 cm or more, more preferably 70 cm or more, higher effects can be exhibited.

<Use>
According to the method disclosed herein, it is possible to efficiently manufacture a laminate in which the pattern of the adhesive pieces is precisely formed on the adherend and the durability of the pattern is excellent. Taking advantage of these features, the methods disclosed herein include exterior materials and interior materials of vehicles, building materials such as exterior materials and interior materials of buildings, window glass, signs, signs, home appliances, optical products, electronic products, etc. The product or a component thereof may be used as an adherend, and such an adherend may be preferably applied to the production of a laminate partially covered by the pattern of the adhesive strip. The laminate may be the various products described above or their constituent members. The adhesive piece is included in various products as a component of the laminate, whereby the adherend included in the laminate, or the product including the laminate or the member thereof, is decorated, displayed, protected, reinforced, It can serve to provide functions such as shock relaxation, stress concentration relaxation, shape maintenance, shape recovery, and the like. The methods disclosed herein can be preferably applied, for example, to the manufacture of FPCs with film cover lays.

  Also, with optical members used for optical products and electronic members used for electronic products, advanced integration, downsizing and weight reduction, and thinning progress has progressed, and a plurality of thin optical members having different coefficients of linear expansion and thickness / Electronic members may be stacked. With such a member as an adherend, by using the method disclosed herein to form a laminate in which the member is partially covered with an adhesive piece, the optical / electronic member has appropriate rigidity. Can be granted. Thereby, in a manufacturing process and / or a product after manufacturing, it is possible to suppress curling and bending due to stress that may occur between a plurality of members having different coefficients of linear expansion and thickness.

  Moreover, in the manufacturing process of the optical product / electronic product, in a phase where the thin optical member / electronic member is subjected to shape processing such as cutting processing as described above, the member (adherend) is partially covered with the adhesive piece. Forming the laminated body, the adhesive piece is utilized as a reinforcing member, and local stress concentration on the optical member / electronic member accompanying the processing of the laminated body is alleviated, and cracks, cracks, laminated members The risk of peeling off can be reduced. Attaching and handling the reinforcing member on the optical member / electronic member also alleviates local stress concentration during transport, lamination, rotation, etc. of the member, and also suppresses bending or bending of the member due to its own weight, etc. It can be useful.

  Furthermore, a device such as an optical product or an electronic product including a laminate in which the adherend is partially covered with the pattern of the adhesive piece is dropped when the device is used by consumers in the market, The adhesive strip included in the device functions as a reinforcing member even when being unintentionally stressed when placed under a heavy object, such as when an alien object collides, etc. Such stress can be relieved and durability can be improved.

  The method disclosed herein is preferably used, for example, to manufacture a laminate in which components of various types of portable devices (portable devices) are adherends, and the members are partially covered with a pattern of adhesive pieces. obtain. Here, "portable" is not enough to be only portable, but means that an individual (a standard adult) has a portability that is relatively easy to carry. Do. In addition, examples of mobile devices here include mobile phones, smartphones, tablet computers, laptop computers, various wearable devices, digital cameras, digital video cameras, audio devices (portable music players, IC recorders, etc.), calculators (computers) Calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, electronic books, in-vehicle information devices, portable radios, portable TVs, portable printers, portable scanners, portable scanners, portable modems, etc. Clocks, flashlights, hand mirrors etc. may be included. Examples of members constituting the portable electronic device may include an optical film, a display panel and the like used in an image display device such as a thin layer display such as a liquid crystal display and a film type display. The method disclosed herein can be preferably applied also to applications in which various members in automobiles, home appliances and the like are used as adherends, and the members are partially covered with a pattern of adhesive pieces.

  The following examples illustrate some of the embodiments of the present invention, but are not intended to limit the present invention to those shown in the specific examples. In the following description, "parts" and "%" are on a weight basis unless otherwise noted.

(Preparation of Polymer A1)
In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet and a condenser, 63 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of N-vinylpyrrolidone (NVP), 9 parts of methyl methacrylate (MMA), 2- Charge 13 parts of hydroxyethyl acrylate (HEA) and 200 parts of ethyl acetate as a polymerization solvent, stir at 60 ° C. under a nitrogen atmosphere for 2 hours, then add 0.2 parts of AIBN as a thermal initiator, The reaction was carried out for a time to obtain a solution of polymer A1. Mw of this polymer A1 was 1.1 million.

(Preparation of Polymer A2)
A solution of polymer A2 was obtained by performing solution polymerization in the same manner as in the synthesis of polymer A1 except that the composition of the monomers used was changed to 2EHA / HEA = 95/5 (weight ratio). Mw of this polymer A2 was 900,000.

(Preparation of Polymer A3)
96.2 parts of 2EHA, 3.8 parts of HEA, and 150 parts of ethyl acetate as a polymerization solvent are charged in a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction pipe and a cooler, and 2 parts under a nitrogen atmosphere at 60 ° C. After stirring for a period of time, 0.2 parts of AIBN was added as a thermal initiator, and reaction was carried out at 60 ° C. for 6 hours to obtain a solution of polymer A3 (solid content: 40%). Mw of this polymer A3 was 540,000.

(Preparation of Polymer B1)
40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), 20 parts of 2-ethylhexyl methacrylate (2EHMA), 900 g / mol of functional group equivalent in a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet and a condenser 9 parts of a polyorganosiloxane skeleton-containing methacrylate monomer (trade name: X-22-174 ASX, manufactured by Shin-Etsu Chemical Co., Ltd.), a polyorganosiloxane skeleton-containing methacrylate monomer having a functional group equivalent of 4600 g / mol (trade name: KF-2012 11 parts of Shin-Etsu Chemical Co., Ltd., 100 parts of ethyl acetate, and 0.6 parts of thioglycerol as a chain transfer agent, stirred at 70 ° C. under a nitrogen atmosphere for 1 hour, AIBN 0 as a thermal initiator After adding 2 parts and reacting at 70 ° C for 3 hours, further add 0.1 weight Was of AIBN introduced, was followed by 5 hours of reaction at 80 ° C.. Thus, a solution of siloxane structure-containing polymer B1 was obtained. Mw of this polymer B1 was 20000.

In addition, the weight average molecular weight of each polymer mentioned above was measured on condition of the following using GPC apparatus (made by Tosoh Corp., HLC-8220GPC), and it calculated | required by polystyrene conversion.
Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
Sample injection volume: 10 μl
-Eluent: THF-Flow rate: 0.6 ml / min
・ Measurement temperature: 40 ° C
·column:
Sample column; TSKguardcolumn SuperHZ-H (one) + TSKgel SuperHZM-H (two)
Reference column; TSKgel SuperH-RC (one)
・ Detector: Differential refractometer (RI)

<Production of adhesive sheet>
(Adhesive sheet D1)
In the solution of the polymer A1, 2.5 parts of the polymer B1 based on solid content per 100 parts of the polymer A1 contained in the solution, an isocyanate crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, 2.5 parts of Mitsui Chemicals, Inc. were added and uniformly mixed to prepare a pressure-sensitive adhesive composition C1.
The adhesive composition C1 is directly applied to one surface of a 75 μm-thick PET film (“Lumirror S10” manufactured by Toray Industries, Inc.) which has not been surface-treated, and heated at 110 ° C. for 2 minutes to be dried. A pressure-sensitive adhesive layer is formed, and on the surface (adhesive surface) of the pressure-sensitive adhesive layer, a release-treated surface of a release liner (MRQ50T100 manufactured by Mitsubishi Chemical Corporation, a polyester film treated on one side with a silicone release agent, thickness 50 μm) It stuck and protected. Thus, a pressure-sensitive adhesive sheet D1 having a pressure-sensitive adhesive layer on one side of a substrate layer made of a PET film having a thickness of 75 μm and having the surface (pressure-sensitive adhesive surface) of the pressure-sensitive adhesive layer protected by a release liner is obtained. The

(Adhesive sheet D2)
An isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) was added to the solution of the polymer A1 based on solid content per 100 parts of the polymer A1 contained in the solution. 5 parts, 30 parts of a photo-curing agent (trade name: A-200, polyethylene glycol # 200 diacrylate, functional group equivalent 154 g / eq, Shin-Nakamura Chemical Co., Ltd.), and 0.1 parts of a photoinitiator are added, By uniformly mixing, a pressure-sensitive adhesive composition C2 was prepared. As a photoinitiator, 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184" from BASF) was used.
Using a fountain roll, directly apply the adhesive composition C2 to one side of a 75 μm-thick PET film (“Lumirror S10” manufactured by Toray Industries, Inc.) that has not been surface-treated, and dry by heating at 130 ° C. for 1 minute As a result, a 25 μm thick adhesive layer was formed. The surface (adhesive surface) of this pressure-sensitive adhesive layer is adhered to a release-treated surface of a release liner (a PET film whose surface is treated with a silicone release agent, 25 μm thick) for protection, and aging for 4 days in an atmosphere of 25 ° C. A treatment was carried out to allow the crosslinking to proceed. Thus, a pressure-sensitive adhesive sheet D2 in a form in which the pressure-sensitive adhesive surface was protected by a release liner was obtained.

(Adhesive sheet D3)
In the solution of the polymer A2, an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemical Co., Ltd.) per 100 parts of the polymer A2 contained in the solution is 2.5 on a solids basis. A part was added and uniformly mixed to prepare a pressure-sensitive adhesive composition C3. A pressure-sensitive adhesive sheet D3 was obtained in the same manner as in the preparation of the pressure-sensitive adhesive sheet D1, except that the pressure-sensitive adhesive composition C3 was used instead of the pressure-sensitive adhesive composition C1, to obtain a pressure-sensitive adhesive sheet D3 in a form in which the pressure-sensitive adhesive surface was protected by a release liner.

(Adhesive sheet D4)
A pressure-sensitive adhesive composition C4 was prepared in the same manner as in the preparation of the pressure-sensitive adhesive composition C1 except that the polymer B1 was not used. A pressure-sensitive adhesive sheet D4 was obtained in the same manner as in the preparation of the pressure-sensitive adhesive sheet D1 except that the pressure-sensitive adhesive composition C4 was used instead of the pressure-sensitive adhesive composition C1, to obtain a pressure-sensitive adhesive sheet D4 in a form in which the adhesive surface was protected by a release liner.

(Adhesive sheet D5)
In the solution of the polymer A3, based on solid content, 2.5 parts of the polymer B1 per 100 parts of the polymer A3 contained in the solution, an isocyanate crosslinking agent (trade name: Coronate L (trimethylolpropane / tolylene diisocyanate) An adhesive composition C5 was prepared by adding 3.3 parts of a 75% ethyl acetate solution of a trimer adduct (manufactured by Tosoh Corporation) and uniformly mixing to prepare an adhesive composition C instead of the adhesive composition C1. In the same manner as in the preparation of the pressure-sensitive adhesive sheet D1 except that C5 was used, a pressure-sensitive adhesive sheet D5 in a form in which the pressure-sensitive adhesive surface was protected by a release liner was obtained.

<Measurement of adhesion to polyimide>
A test for measuring adhesion by fixing a 12.5 μm thick polyimide film ("Kapton 50EN" manufactured by Toray DuPont) to a glass plate via a double-sided adhesive tape ("No. 531" manufactured by Nitto Denko Corporation) A piece was made. In addition, adhesive sheets D1 to D4 and D5 were cut into strips 25 mm wide to prepare measurement samples.
In a standard environment of 23 ° C. and 50% RH, the adhesive surface of the measurement sample was crimped to the test piece by reciprocating a 2 kg roller once. After leaving this for 30 minutes under the above standard environment, using a tensile tester (“TCM-1kNB” manufactured by Minebea Co., Ltd.), peeling is performed under the conditions of 180 ° peeling angle and 300 mm / min tensile speed according to JIS Z0237. The strength (initial adhesion) B ₀ [N / 25 mm] was measured.
Further, in the measurement of initial adhesion B _0, changing the time left in a standard environment after crimping the test sample to the test piece 12 and 24 hours. Otherwise in the same manner as in the measurement of the initial adhesion _{B 0,} it was measured 12 hours after adhesion at room temperature [N / 25 mm] and at room temperature for 24 hours after adhesion [N / 25mm].
Furthermore, the measurement sample is crimped to the test piece in the same manner as in the measurement of the initial tackiness B ₀ and held for about 4 weeks under a fluorescent lamp at normal temperature (about 25 ° C. here), and then the measurement of the initial tackiness B ₀ The peel strength (adhesive strength after 4 weeks) [N / 25 mm] was measured in the same manner as in.

Further, the measurement sample prepared from the adhesive sheets D1 and D5 was pressure-bonded to the test piece in the same manner as the measurement of the initial adhesive strength B ₀ , left in the above standard environment for 30 minutes, and heated at 80 ° C. for 5 minutes . Further, after left to stand under the above standard environment for 30 minutes, the peel strength (adhesive strength after heating) [N / 25 mm] was similarly measured at a peel angle of 180 degrees and a tensile speed of 300 mm / min. It was 5.45 N / 25 mm in .94 N / 25 mm and the adhesive sheet D5.
Further, a measurement sample prepared from the adhesive sheet D2 is crimped to a test piece in the same manner as the measurement of the initial adhesive strength B ₀ , and left for 30 minutes under the above standard environment, and then using Ushio UniField. Ultraviolet light having a dominant wavelength of about 365 nm was irradiated to have a light quantity of 2000 mJ / cm ² . Furthermore, after left to stand under the above standard environment for 30 minutes, the peel strength (adhesive force after UV irradiation) [N / 25 mm] was similarly measured at a peel angle of 180 degrees and a tensile speed of 300 mm / min. It was 25 mm.

<Production of laminates>
(Production Example 1)
The pressure-sensitive adhesive sheet D1 was cut into a size of 25 mm wide and 100 mm long to prepare a pressure-sensitive adhesive sheet for producing a laminate. Further, as an adherend, a polyimide film having a thickness of 12.5 μm, a width of 30 mm, and a length of 120 mm ("Kapton 50EN" manufactured by Toray Dupont Co., Ltd.) was prepared.
The center of the adherend was aligned with the center of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive sheet was attached to the adherend by a hand roller (sticking step).
The cutting step was performed after the adhesive sheet was attached to the adherend and before the following partial removal step. A second region of 2 mm in width and 100 mm in length extending linearly from one end of the adhesive sheet in the longitudinal direction to the other end is set at the width center of the adhesive sheet in the obtained adhesive sheet / adherend laminate. By irradiating a laser from the adhesive sheet surface side along the boundary (two straight lines) between the second area and the first area on both sides thereof, a cutting process was performed to cut only the adhesive sheet D1. The above-mentioned cutting process was performed under the following conditions using a laser cutting apparatus "Spirit, Model number SI-30V" manufactured by GCC.
Speed: 9.0%
Power: 10.0%
DPI: 500
PPI: 400
About 12 hours after the adhesive sheet was attached to the adherend, a partial removal process was performed. Specifically, one end of the second region is peeled off from the adherend, gripped by the chuck of a tensile tester, and pulled in the longitudinal direction of the adhesive sheet at a peeling angle of 180 degrees and a tensile speed of 300 mm / min. The slit-like second region was peeled off from the adherend.
Then, by performing the above-mentioned heating (at 80 ° C. for 5 minutes) as an adhesion raising stimulus (adhesion raising step), the target laminate, ie, the adherend described above is covered with the above-mentioned adhesive sheet subjected to the pattern processing The laminated body of the different structure was produced. Table 1 shows the adhesion value of adhesive sheet D1 after room temperature for 12 hours as the adhesive strength in the partial removal step of Production Example 1, and the adhesion value of adhesive sheet D1 after heating as the adhesive strength of the laminate. doing.

(Production Example 2)
Except using the pressure-sensitive adhesive sheet D2 instead of the pressure-sensitive adhesive sheet D1 and changing the stimulation applied in the adhesion raising step from heating to the above-mentioned UV irradiation (main wavelength about 365 nm, light quantity 2000 mJ / cm ² ), A laminate was produced in the same manner as in Production Example 1. Table 1 shows the adhesion value of the adhesive sheet D2 after room temperature for 12 hours as the adhesion in the partial removal step of Production Example 2, and the adhesion value of the adhesive sheet D2 after UV irradiation as the adhesion of the laminate. Described.

(Production Examples 3 and 4)
After using the pressure-sensitive adhesive sheet shown in Table 1, after the cutting process, neither the above-mentioned heating nor UV irradiation is performed, but instead the elapsed time from the application to the adherend of the pressure-sensitive adhesive sheet becomes 24 hours It was left under the above-mentioned standard environment. A laminate was produced in the same manner as in Production Example 1 except for the above. Table 1 shows the adhesive strength of each adhesive sheet after room temperature 12 hours as the adhesive strength in the partial removal step of Production Examples 3 and 4, and the adhesive strength of each adhesive sheet after room temperature 24 hours as the adhesive strength of the laminate. The value of is stated.

(Production Example 5)
In Production Example 1, about 11 hours after the adhesive sheet D1 is attached to the adherend, the above-mentioned heating (80 ° C., 5 minutes) is performed, and then the elapsed time after the adhesive sheet D1 is attached to the adherend A partial removal step was performed after keeping at room temperature until about 12 hours. A laminate was manufactured in the same manner as in Production Example 1 with respect to the other points. In Table 1, the value of the adhesion after heating of the pressure-sensitive adhesive sheet D2 is described as the adhesion in the partial removal step of Production Example 5.

(Production Examples 6 and 7)
The adhesive sheets D1 and D2 are attached to the adherend in the same manner as in Production Example 1 and left under a fluorescent lamp for about 24 hours in the room maintained in the above-mentioned standard environment. A removal step was performed. Thereafter, the laminates according to Production Examples 6 and 7 are obtained by holding under the fluorescent lamp in the room of the standard environment until the elapsed time from sticking the adhesive sheets D1 and D2 to the adherend is 4 weeks. Obtained. Table 1 shows the adhesive strength after 24 hours of room temperature of each adhesive sheet as the adhesive strength in the partial removal step of Production Examples 6 and 7 and the adhesive strength of each adhesive sheet after 4 weeks as the adhesive strength of the laminate. The values are listed.

Production Example 8
A laminate was produced in the same manner as in Production Example 1 except that the pressure-sensitive adhesive sheet D1 was used instead of the pressure-sensitive adhesive sheet D1. Table 1 shows the adhesion value of adhesive sheet D5 after room temperature for 12 hours as the adhesion in the partial removal step of Production Example 8, and the adhesion value of adhesive sheet D5 after heating as the adhesion of the laminate. doing.

(Slit part removability evaluation)
In the partial removal process of each manufacturing example, when no deformation such as elongation is observed in the adherend when peeling the second region from the adherend, “G” (pattern processability is good), the deformation is When it was recognized, it was evaluated as "P" (poor pattern processability). The results are shown in Table 1.
In addition, since the peeling of 2nd area | region was not able to be performed appropriately in the manufacture examples 4 and 5, the following durability tests were not done. In addition, in any of Production Examples 1 to 3 and 6, 7, and 8, no adhesive residue on the adherend or contamination of the adherend was observed when the second region was peeled off.

(Durability test)
With respect to the laminates obtained in Production Examples 1 to 3 and 6, 7 and 8, a planar body no-load U-shaped stretch tester "DLDM 111 LH" manufactured by Yuasa System Instruments Co., Ltd. and a jig (planar body no-load U-shaped stretch Using the test jig, the durability test was carried out under conditions of an expansion / contraction speed of 30 rpm, a bending radius of 3 mm, and a number of expansion / contraction times of 100 times.
Specifically, as shown in FIG. 6, after both ends x, y of the sample 60 are fixed to the clamp portions 61, 62 of the above-mentioned testing machine with a double-sided tape (not shown), the sample 60 under the above conditions. From the state of a plane, the adhesive sheet side was made inside and the expansion-contraction which bends in U shape of a bending radius of 3 mm was performed repeatedly. When bending the sample 60, both ends x and y of the sample 60 are brought into contact with each other by the operation of the clamp, and the other parts of the sample 60 are pinched from both sides without load by plate parts 63 and 64 separately installed. I did it.
The state of the sample after 100 times of expansion and contraction was visually observed, and if no floating was observed between the adhesive sheet and the adherend, "G" (good durability), if "floating" was observed, "P" It was evaluated as (poor durability). The results are shown in Table 1.

  As shown in Table 1, among the production examples 1, 2, 4 to 7 according to the production of a laminate having an adhesive strength of 5 N / 25 mm, a partial removal process before the adhesive strength exceeds 2 N / 25 mm In each of Production Examples 1, 2, 6, 7, and 8 in which the second region was peeled off in the partial removal step, the laminates produced exhibited good durability. Particularly good results were obtained in Production Examples 1, 2, 6, 7 in which laminates were produced using pressure-sensitive adhesive sheets D1 and D2 provided with a pressure-sensitive adhesive layer containing polymer A1 in which N-vinyl cyclic amide is copolymerized. It was done. On the other hand, in the manufacturing example 3, the durability of the obtained laminate was low, and in the manufacturing examples 4 and 5, there was a problem in the peelability of the second region in the partial removing step.

  As mentioned above, although the specific example of this invention was described in detail, these are only an illustration and do not limit a claim. The art set forth in the claims includes various variations and modifications of the specific examples illustrated above.

Further, the matters disclosed by this specification include the following.
(1) A manufacturing method of a laminate including an adherend and an adhesive piece partially covering the adherend, wherein the adhesive strength of the adhesive piece to the adherend is 5 N / 25 mm or more,
Affixing step of adhering a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the adherend-side surface of the base material layer to the adherend;
A cutting step of performing cutting on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece in the adhesive sheet;
Partially removing the second region from the adherend while leaving the first region on the adherend;
In this order,
Here, the method for manufacturing a laminate, wherein the partial removal step is performed before the adhesive force of the pressure-sensitive adhesive sheet to the adherend exceeds 2 N / 25 mm.
(2) The method for producing a laminate according to the above (1), wherein the adhesive sheet has a tackiness of 2 N / 25 mm or less after 24 hours at 23 ° C. after laminating to polyimide.
(3) The method for producing a laminate according to the above (1) or (2), wherein heat treatment is performed after the partial removal step to make the adhesive strength of the first region to the adherend 5N / 25 mm or more. .
(4) The pressure-sensitive adhesive layer contains the polymer A having a glass transition temperature of less than 0 ° C., and the polymer B which is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer. The laminated body manufacturing method as described in (3).
(5) The laminate according to the above (1) or (2), wherein the adhesive strength of the first region to the adherend is 5 N / 25 mm or more by performing ultraviolet irradiation treatment after the partial removal step. Method.
(6) The pressure-sensitive adhesive layer comprises a photocurable composition containing a base polymer and a photocuring agent,
The photo-curing agent is a polyfunctional (meth) acrylate,
The method for producing a laminate according to (5), wherein a content of the photo-curing agent is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the base polymer.
(7) The laminate according to (1) or (2), which is stored at normal temperature until the adhesion of the first region to the adherend after the partial removal step is 5 N / 25 mm or more. Method.
(8) The thickness of the pressure-sensitive adhesive sheet is 30 μm or more, and the thickness Ts of the base material layer is twice or more the thickness Ta of the pressure-sensitive adhesive layer. The laminated body manufacturing method in any one.
(9) The method for producing a laminate according to any one of (1) to (8), wherein the second region is set such that at least one end of the second region reaches the end of the pressure-sensitive adhesive sheet.
(10) The method for producing a laminate according to (9), wherein the second region has a shape in which one end reaching the end of the pressure-sensitive adhesive sheet becomes wider toward the end of the pressure-sensitive adhesive sheet.
(11) The laminate according to any one of (1) to (10), wherein the pressure-sensitive adhesive sheet used in the sticking step has an area of 2500 cm ² or more and a short side length of 50 cm or more. Production method.
(12) As the pressure-sensitive adhesive sheet and the adherend used in the sticking step, one containing a plurality of units corresponding to the laminate is used,
The laminated body manufacturing method in any one of said (1)-(11) which further includes the division process which divides the said adhesive sheet and the said to-be-adhered body into the said unit as a process performed after the said sticking process.
(13) An apparatus for performing the manufacturing method according to any one of the above (1) to (12),
A sticking mechanism for sticking the above-mentioned pressure-sensitive adhesive sheet,
A cutting mechanism for cutting the adhesive sheet;
A peeling mechanism for peeling the second region of the pressure-sensitive adhesive sheet,
Laminate manufacturing apparatus including:

DESCRIPTION OF SYMBOLS 1 laminated body 10 adherend 10A surface 20 adhesive sheet 21 1st area | region 21A, 21B adhesive piece 22 2nd area | region 202 base material layer 204 adhesive layer 50 laminated body manufacturing apparatus 51 sticking mechanism 52 cutting mechanism 53 peeling mechanism

Claims (10)

A manufacturing method of a laminate including an adherend and an adhesive piece partially covering the adherend, wherein the adhesive strength of the adhesive piece to the adherend is 5 N / 25 mm or more,
Affixing step of adhering a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface of the base material layer on the adherend side to the adherend;
A cutting step of performing cutting on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece in the adhesive sheet;
Partially removing the second region from the adherend while leaving the first region on the adherend;
In this order,
Here, the pressure-sensitive adhesive layer contains a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B which is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer.
The monomer component constituting the polymer A contains N-vinyl cyclic amide,
The partial removal step is performed before the adhesion of the pressure-sensitive adhesive sheet to the adherend exceeds 2N / 25 mm.
The laminated body manufacturing method which heat-processes after the said partial removal process, and makes the adhesive force with respect to the said to-be-adhered body of the said 1st area | region be 5 N / 25 mm or more.   The laminated body manufacturing method of Claim 1 in which the monomer component which comprises the said polymer A contains a hydroxyl-containing monomer further. A manufacturing method of a laminate including an adherend and an adhesive piece partially covering the adherend, wherein the adhesive strength of the adhesive piece to the adherend is 5 N / 25 mm or more,
Affixing step of adhering a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface of the base material layer on the adherend side to the adherend;
A cutting step of performing cutting on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece in the adhesive sheet;
Partially removing the second region from the adherend while leaving the first region on the adherend;
In this order,
Here, the pressure-sensitive adhesive layer contains a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B which is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer.
The monomer component constituting the polymer A contains N-vinyl cyclic amide,
The partial removal step is performed before the adhesion of the pressure-sensitive adhesive sheet to the adherend exceeds 2N / 25 mm.
The laminated body manufacturing method to store at normal temperature until the adhesive force with respect to the said to-be-adhered body of the said 1st area | region becomes 5 N / 25 mm or more after the said partial removal process.   The laminate according to any one of claims 1 to 3, wherein as the pressure-sensitive adhesive sheet, one having an adhesion of 2 N / 25 mm or less after 24 hours at 23 ° C. after bonding to polyimide is used. Method.   The thickness of the said adhesive sheet is 30 micrometers or more, and thickness Ts of the said base material layer is 2 times or more of thickness Ta of the said adhesive layer, It is described in any one of Claim 1 to 4 Laminate manufacturing method.   The laminate manufacturing method according to any one of claims 1 to 5, wherein the second area is set such that at least one end of the second area reaches an end of the pressure-sensitive adhesive sheet.   The laminate manufacturing method according to claim 6, wherein the second region is shaped such that one end reaching the end of the pressure-sensitive adhesive sheet becomes wider toward the end of the pressure-sensitive adhesive sheet. The method for producing a laminate according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive sheet used in the sticking step has an area of 2500 cm ² or more and a short side length of 50 cm or more. As the pressure-sensitive adhesive sheet and the adherend used in the pasting step, one containing a plurality of units corresponding to the laminate is used.
The laminate manufacturing method according to any one of claims 1 to 8, further comprising a dividing step of dividing the pressure-sensitive adhesive sheet and the adherend into the units as a step performed after the attaching step. An apparatus for carrying out the manufacturing method according to any one of claims 1 to 9,
A sticking mechanism for sticking the pressure-sensitive adhesive sheet,
A cutting mechanism for cutting the adhesive sheet;
A peeling mechanism for peeling the second area of the pressure-sensitive adhesive sheet;
Laminate manufacturing apparatus including:

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