JP6595083B2 - Manufacturing method of laminate - Google Patents

Description

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

  According to the laminate in which the adherend is partially covered with the adhesive piece by attaching one or two or more adhesive pieces to the adherend, various patterns can be formed according to the outer shape and arrangement of the adhesive. Can be expressed. As a method of manufacturing a laminate in which the adherend is partially covered with an adhesive piece in this way, the adhesive sheet can be shaped into a desired adhesive piece shape, for example, by laminating a cover lay film on 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 given as a technical document related to this type of technology.

JP 2013-38379 A

  However, in the above-described method, since the adhesive sheet is cut into a desired adhesive piece shape in advance, and then aligned and bonded to a predetermined adherend site, an error in both the cutting accuracy and the bonding accuracy. Occurs. For this reason, there is a concern that in order to manufacture products with high yield in the manufacture of electronic components that will be miniaturized and refined in the future, very expensive equipment is required. 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 highly adhesive pressure-sensitive adhesive piece to produce a highly durable laminate, the difficulty of the operation of accurately attaching the pressure-sensitive adhesive piece to the adherend tends to increase.

  Then, this invention aims at providing the method of manufacturing efficiently the laminated body by which the pattern by the adhesive piece was accurately formed on the to-be-adhered body, and this adhesive piece was firmly joined to the to-be-adhered body. . Another related invention is to provide an apparatus suitable for carrying out such a manufacturing method.

  According to this specification, there is provided a method for producing a laminate including an adherend and an adhesive piece that partially covers the adherend, and the adhesive strength of the adhesive piece to the adherend is 5 N / 25 mm or more. The The laminate manufacturing method includes a step of attaching 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 to the adherend, and the pressure-sensitive adhesive sheet. A cutting step for cutting a boundary between a first region constituting the adhesive piece and a 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 and removing from the adherend in this order. Here, the partial removal step is performed before the adhesive strength of the adhesive sheet to the adherend exceeds 2 N / 25 mm.

  According to the manufacturing method described above, the first region is efficiently arranged on the adherend with good shape accuracy and position accuracy by performing the pasting step, the cutting step, and the partial removal step in this order. Obtainable. In addition, since the partial removal step is performed before the adhesive force of the adhesive sheet to the adherend exceeds 2 N / 25 mm, it is easy to perform an operation of peeling the second region from the adherend, Damage is less likely to occur.

  In some embodiments, as the pressure-sensitive adhesive sheet, one having an adhesive strength of 2 N / 25 mm or less after 24 hours at 23 ° C. after being bonded to polyimide can be preferably used. According to such an adhesive sheet, it can respond flexibly to the lead time of the manufacturing process of the laminate.

  In some aspects of the laminated body manufacturing method disclosed herein, heat treatment is performed after the partial removal step so that the adhesive strength of the first region to the adherend is 5 N / 25 mm or more. Such an aspect includes, for example, a pressure-sensitive adhesive layer containing a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B that is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer. However, the present invention is not limited to this.

  In some embodiments, the monomer component constituting the polymer A may include an N-vinyl cyclic amide. Thus, since the pressure-sensitive adhesive sheet using the polymer A having a composition containing N-vinyl cyclic amide as a constituent monomer component can exhibit good adhesive strength increasing properties, it is preferably used for carrying out the production method disclosed herein. obtain.

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

Moreover, the laminated body manufacturing method disclosed here is carried out in a mode in which after the partial removal step, the laminate is stored at room temperature until the adhesive strength of the first region to the adherend is 5 N / 25 mm or more. Also good.
In this specification, normal temperature means a temperature of approximately 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 material layer that is twice or more the thickness Ta of the pressure-sensitive adhesive layer can be preferably used. . By using such an adhesive sheet, there is an advantage that it is easy to perform an operation of attaching to an adherend and a peeling operation of the second region.

  The second region is preferably set so that at least one end thereof reaches the end of the pressure-sensitive adhesive sheet. This provides an advantage that the second region can be easily picked up when the partial removal process is performed. From the viewpoint of improving pickup properties, 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.

The production method disclosed herein can be preferably carried out in a mode in which an adhesive sheet having an area of 2500 cm ² or more and a short side length of 50 cm or more is used in the pasting step. Thus, in the aspect which uses an adhesive sheet with a large area and a wide width, the advantage by employ | adopting the manufacturing method disclosed here can be exhibited more effectively.

  The manufacturing method disclosed herein uses, as the pressure-sensitive adhesive sheet and the adherend used in the pasting step, those including a plurality of units corresponding to the laminate, and a step performed after the pasting step, A dividing step of dividing the pressure-sensitive adhesive sheet and the adherend into the units may be further included. Thus, a plurality of laminates can be efficiently manufactured by dividing the adhesive sheet including a plurality of units after being attached to an adherend. The configurations of the plurality of units may be the same or different.

  According to this specification, an apparatus for manufacturing a laminate including an adherend and an adhesive piece partially laminated on the adherend is provided. The apparatus includes an attaching mechanism for attaching an adhesive sheet. The device may include a cutting mechanism that performs a cutting process on the pressure-sensitive adhesive sheet. The apparatus may include a peeling mechanism that peels off the second region. Using the manufacturing apparatus having such a configuration, any one of the laminate manufacturing methods disclosed herein can be suitably implemented.

  A combination of the above-described elements as appropriate can also be included in the scope of the invention for which protection by patent is sought by this 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 explanatory drawing which shows schematic structure of the laminated body manufacturing apparatus used for the laminated body manufacturing method which concerns on 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 those specifically mentioned in the present specification and necessary for the implementation of the present invention are based on the teachings on the implementation of the invention described in the present specification and the common general technical knowledge at the time of filing. It can be understood by a trader. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.
In the following drawings, members / parts having the same action may be described with the same reference numerals, and redundant descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematically illustrated in order to clearly describe the present invention, and do not necessarily accurately represent actual sizes and scales.

<< Manufacturing Method of Laminate >>
FIG. 1 is a flowchart showing a laminate manufacturing method according to an embodiment, FIG. 2 is a perspective view showing a laminate manufactured by the method, and FIG. 3 is a sectional view taken along the 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 21 </ b> A and 21 </ b> B that partially cover the surface 10 </ b> A of the adherend 10. The adhesive strips 21A and 21B are formed by attaching the adhesive sheet 20 to the adherend 10 and then leaving the first region 21 on the adherend 10 and leaving the second region 22 from the adherend 10. It is formed from the first region 21 left on the adherend 10 by peeling and removing. The pressure-sensitive adhesive sheet 20 has a configuration in which a pressure-sensitive adhesive layer 204 is laminated on one side of a base material layer 202.

As shown in FIG. 1, the laminate manufacturing method according to this embodiment includes a pasting step S10, a cutting step S20, and a partial removing step S30 in this order.
In the pasting step S10, the adhesive sheet 20 is pasted on the adherend 10. The pressure-sensitive adhesive sheet 20 used in this step is not a component of the laminate 1 and the first region 21 which is a region that will be included in the component of the laminate 1 as the adhesive pieces 21A and 21B. And the second region 22 used only in the manufacturing process. In the example shown in FIG. 2, a second region 22 that extends linearly from one end to the other end in the longitudinal direction of the pressure-sensitive adhesive sheet 20 is set at substantially the center of the width of the pressure-sensitive adhesive sheet 20. In the adhesive sheet 20 used in the pasting step S10, the first area 21 and the second area 22 are physically connected, and these areas 21 and 22 can be handled as a continuous adhesive sheet 20.

In the cutting step S <b> 20, a cutting process is performed on the boundary between the first region 21 and the second region 22 of the pressure-sensitive adhesive sheet 20 attached to the adherend 10. For example, as shown in FIG. 4, laser cutting is performed by irradiating laser light L along a planned cutting line C that forms the boundary between the first region 21 and the second region 22. Although FIG. 4 shows an example of laser cutting, the cutting means 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 CO ₂ laser and YAG laser; cutting with a blade such as Thomson blade, pinnacle blade, rotary blade, knife; blade cutting; It is not limited to these. A cutting | disconnection means can be used individually by 1 type or in combination of 2 or more types.

  The partial removal step S30 is performed before the adhesive strength of the adhesive sheet adhered to the adherend in the pasting step exceeds 2 N / 25 mm (in other words, after pasting, the adhesive strength is 2 N / 25 mm or less). To be done). In the partial removal step S <b> 30, 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 toward the other end. As a result, as shown in FIGS. 2 and 3, the adhesive strips 21A and 21B formed from the first region 21 are spaced apart from each other on the adherend 10, and the adhesive strips 21A and 21B are covered with each other. A structure in which the body 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. Then, a coating pattern composed of two adhesive pieces 21A and 21B that are arranged 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 spaced apart from each other in the laminate 1 can be attached to the adherend 10 in the form of a single adhesive sheet 20 and adhesive. Since the adjustment of the relative positional relationship between the adhesive piece 21A and the adhesive piece 21B is not required when the sheet 20 is attached, the manufacturing efficiency of the laminate 1 is improved. Moreover, since the cutting process is performed on the boundary between the first region 21 and the second region 22 of the pressure-sensitive adhesive sheet 20 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 positional accuracy with respect to 10. For example, in the pasting step S10, when the adhesive sheet 20 is slightly misaligned with the adherend 10 or when the adhesive sheet 20 is slightly expanded or contracted due to a change in temperature, release of internal stress, or the like. In addition, by adjusting the position and shape of the cutting process in the cutting step S20, those effects can be eliminated or reduced.

  In the said manufacturing method, the laminated body 1 whose adhesive force with respect to the adherend of adhesive piece 21A, 21B is 5 N / 25mm or more is manufactured. The adhesive pieces 21A and 21B are firmly bonded to the adherend 10 in this way because external force such as contact with a human hand, deformation of the adherend, or the laminate when the laminate 1 is used. Is preferable from the viewpoint of suppressing the phenomenon in which the adhesive strips 21A and 21B are peeled off or floated from the adherend 10 due to environmental factors such as exposure to wind and rain or temperature changes. On the other hand, if the adhesiveness of the second region 22 to the adherend 10 is too high in the partial removal step S30, the adherend 10 may be deformed such as stretch or damaged such as surface peeling when the second region 22 is peeled off. Or the second region 22 may be broken during the peeling. According to the manufacturing method described above, the adhesive strip 21A is obtained by performing the partial removal step S30 before the adhesive strength of the adhesive sheet attached to the adherend in the attaching step S10 exceeds 2 N / 25 mm. , 21B can be manufactured to be firmly bonded to the adherend 10, and the above-described 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, 1.3 N / 25 mm or less, 1 N / 25 mm or less, or 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, or 0.2 N / 25 mm or more.

The manufacturing method disclosed here uses an adhesive sheet having an adhesive strength after 24 hours at 23 ° C. (hereinafter also referred to as an adhesive strength after 24 hours at room temperature) of 2 N / 25 mm or less after being bonded to polyimide. Can be preferably implemented. According to such an adhesive sheet, it can respond flexibly to 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 performing partial removal process S30, you may further perform adhesive force raise process S40 which raises the adhesive force with respect to the to-be-adhered body 10 of adhesive piece 21A, 21B as needed. According to the manufacturing method including such an adhesive force increasing step, it is possible to shorten a period until a target laminated body (that is, a laminated body in which the adhesive strength of the adhesive piece to the adherend is 5 N / 25 mm or more) is obtained. This can improve the productivity of the laminate. Moreover, it exists in the tendency for the laminated body with higher adhesive force with respect to the adherend of an adhesive piece to be manufactured by performing the said adhesive force raise process.

  The adhesive strength increasing step S40 may be a step of giving a stimulus that promotes an increase in the adhesive strength of the adhesive strips 21A and 21B. The content of the stimulus can be appropriately selected according to the type of pressure-sensitive adhesive sheet used. Examples of the stimulation may include heating, irradiation with actinic rays, 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 pressure-sensitive adhesive sheet to be used, the desired productivity and performance of the laminate, and the manufacturing equipment and cost of the laminate. It is an arbitrary process that can be appropriately adopted in consideration of the above. For example, by the appropriate selection of the pressure-sensitive adhesive sheet used for the production of the laminate, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet to the adherend before the partial removal step is not performed after the partial removal step. In addition, a laminated body in which a partial removal step is performed and the adhesive strength of the adhesive sheet to the adherend is 5 N / 25 mm or more can be produced.

  The pressure-sensitive adhesive piece included in the laminate produced by the method disclosed herein includes a base material layer and a pressure-sensitive adhesive layer, and is bonded to the adherend via the pressure-sensitive adhesive layer. Thus, in the obtained laminate, the adhesive piece and the adherend are bonded 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, low temperature characteristics, adhesion between the adherend and the adhesive piece, and the like of the produced laminate.

  In the example shown in FIG. 2, an adhesive sheet 20 having the same size as that of the adherend 10 is attached so as to cover the entire surface (entire region) on one side of the adherend 10. The sticking mode of the pressure-sensitive adhesive sheet is not limited to this. For example, the adhesive sheet may be attached so as to cover only a partial region on one side of the adherend, or may be attached so that a part of the adhesive sheet protrudes from the adherend. Moreover, in the adhesive sheet used for sticking process S10, the 1st area | region and the 2nd area | region should just be connected to the grade which can handle these area | regions as a continuous sheet | seat. It is not hindered that cutting assist structures such as cuts (perforations, etc.) and half cuts are provided at the boundary with the two regions. Here, the half cut refers to a cut having a depth that does not penetrate the adhesive sheet in the thickness direction, and is typically formed as a cut having a depth that does not penetrate the base material layer in the thickness direction. Such an incision can be formed, for example, by allowing the processing blade to enter from the back surface of the base material layer (the side opposite to the side on which the adhesive layer is laminated) to a depth that does not penetrate the base material layer. In one embodiment, from the viewpoint of improving the handleability of the pressure-sensitive adhesive sheet and reducing the manufacturing cost, a pressure-sensitive adhesive sheet in which a cutting assist structure is not provided at the boundary between the first region and the second region can be preferably used. Moreover, the mark useful for position alignment with this adhesive sheet and a to-be-adhered body may be provided in the adhesive sheet used for sticking process S10. The mark may be a structural mark such as a through hole, a notch, a dent, or the like, or a visual mark such as an optically detectable mark (for example, printing or coloring). , It may be based on the arrangement of different members (for example, attaching an identification label, fixing an element that enables signal transmission or reflection). Such a mark may be provided in one or both of the first region and the second region, or may be provided at the boundary between the first region and the second region.

  In the example shown in FIG. 4, in the cutting step S <b> 20, continuous linear cutting is performed at a depth reaching the adherend surface through the pressure-sensitive adhesive sheet, but the cutting process is limited to this. Not. For example, the first region and the second region after the cutting step S20 may be partially connected as long as the partial removal step S30 can be appropriately performed. Examples of such cutting processes include discontinuous cutting processes such as perforations, half-cut processes, processes that combine perforations and half-cuts (for example, a cut that penetrates a base material layer, and the base material layer And a cutting process in which the depth of not-penetrating depth is alternately repeated). The cutting process may be performed at a depth that penetrates the adhesive sheet and reaches the surface of the adherend, and is performed so as to penetrate the adhesive sheet and further reach a partial depth from the surface of the adherend. It may be performed at a depth that does not penetrate the adhesive sheet (that is, half cut). In the manufacturing method disclosed herein, since the adhesive force of the adhesive sheet to the adherend is suppressed low when performing the partial removal step S30, the first region is at least deep through the base material layer. It is preferable to perform the cutting process so that the second region and the second region are completely separated. This can be advantageous from the viewpoints of improving the pickup performance of the second region in the partial removal step S30, preventing the first region from being lifted and shifted, 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 second region extending linearly reach the end of the adhesive sheet. Thus, it is preferable from a viewpoint of the pick-up property of the 2nd area | region in partial removal process S30 to set this 2nd area | region so that at least one end of a 2nd area | region may reach the edge of an adhesive sheet. In an embodiment in which the second region does not reach the end of the adhesive sheet, for example, the second region is picked up by sticking and lifting a strong adhesive tape on the back of the second region at one end of the second region. Can do. Such a pickup method can also be employed in an embodiment 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 strength of the adhesive sheet to the adherend during the partial removal step is 2 N / 25 mm or less, as described above, by sticking and lifting the adhesive tape. This is advantageous from the viewpoint of improving the pickup performance of the second region.

  In the aspect in which the second region is set to reach the end of the pressure-sensitive adhesive sheet, the width from which the second region reaches the end of the pressure-sensitive adhesive sheet is preferably 0.2 mm or more from the viewpoint of pickup properties. It may be 0.5 mm or more, or 1 mm or more. In order to improve the pick-up property, the second region may be configured such that the width of the second region is increased in the vicinity of the second region reaching the end of the adhesive sheet. In addition, from the viewpoint of miniaturization of a product (electronic device or the like) including a laminate obtained by the manufacturing method disclosed herein, the width from which the second region reaches the end of the pressure-sensitive adhesive sheet may be 10 mm or less. Preferably, it is 8 mm or less.

When the laminate manufacturing method disclosed herein includes an adhesive strength increasing step, the degree of increasing the adhesive strength in the step is not particularly limited, and the adhesive strength after the step or the adhesive strength before the step is not limited. The adhesive force of the laminated body obtained through this process should just be relatively high. In some embodiments, the adhesion increasing step includes adhesion A ₀ [N / 25 mm] to the adherend before the process and adhesion A ₁ [N / 25 mm] to the adherend after the process. Is preferably performed so that the ratio (A ₁ / A ₀ ) ≧ 2. That is, in the adhesive strength increasing step, it is preferable to increase the adhesive strength of the adhesive sheet to the adherend to twice or more that before the step. According to such an adhesive strength increasing step, the ease of removing 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 preferably 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 ratio (A ₁ / A ₀ ) is not particularly limited, it is usually 10,000 or less, 5,000 or less, or 2,000 or less from the viewpoint of suppressing the positional displacement and floating of the first region before the adhesive strength increasing step. Is preferred. Each of the above adhesive strengths A ₀ and A ₁ is an adherend of an adhesive sheet under the conditions of a peel 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 be grasped by measuring the peel 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 manufactured by the method disclosed herein, the adhesive force A _F of the adhesive piece to the adherend may be, for example, more than 5 N / 25 mm, 7 N / 25 mm or more, or 10 N / 25 mm or more. 12N / 25 mm or more. A high adhesive strength A _F is preferable from the viewpoint of suppressing peeling and lifting of the adhesive piece from the adherend during use of the laminate. The upper limit of the adhesive force _AF is not particularly limited. In view of facilitating coexistence with ease of peeling of the second region in the partial removal step, in some embodiments, the adhesive force A _F 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 adhesive strength increasing step, the adhesive strength A ₁ [N / 25 mm] to the adherend of the adhesive sheet after the adhesive strength increasing step is, for example, the adherend of the adhesive strip in the manufactured laminate. It may be approximately the same as the adhesive force A to _F. 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 pressure-sensitive adhesive sheet in the pressure-sensitive adhesive strength increasing step is, for example, a pressure-sensitive adhesive strength increase ratio (B ₁ / B) defined as a ratio of the initial pressure-sensitive adhesive strength B _{0 to} the post-stimulation pressure-sensitive adhesive strength B _{1 0} ) can be set to satisfy a predetermined target value. The initial adhesive strength B ₀ and the post-stimulation adhesive strength B ₁ are measured by the methods described in Examples described later.

In the case where the production method disclosed herein includes an adhesive strength increasing step, the adhesive strength increasing step is preferably performed such that the adhesive strength increasing ratio (B ₁ / B ₀ ) is 2 or more, for example. More preferably, 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 pressure-sensitive adhesive sheet and the adherend and improving the productivity of the laminate, the pressure-sensitive adhesive strength increasing step has a pressure-sensitive adhesive strength increase ratio (B ₁ / B ₀ ) of about 10,000 or less, 5000 or less, or 2000 or less. Can be implemented. In some embodiments, the adhesive strength increase ratio (B ₁ / B ₀ ) may be, for example, 1000 or less, 500 or less, 200 or less, or 100 or less.

In addition, in a flexible display panel, a flexible printed wiring board (FPC), a device in which a display panel and a wiring board are integrated, a flexible substrate material is used, and from the viewpoint of heat resistance and dimensional stability, A polyimide film is often used as the substrate material. The pressure-sensitive adhesive sheet showing the above-mentioned pressure-sensitive adhesive strength B ₀ , B ₁ or pressure-sensitive adhesive strength increase ratio (B ₁ / B ₀ ) with respect to polyimide is used in the production of a laminate in the form of using polyimide as an adherend. In the part removing step, the second region can be easily peeled, and when the obtained laminate is used, it can exhibit the property of excellent adhesion reliability with the adherend. By utilizing this property, an FPC film coverlay can be formed with high accuracy and efficiency. Therefore, the method disclosed here can be preferably applied to, for example, the manufacture of an FPC having a film coverlay.

  The heating temperature in the case of heating as a stimulus given to the pressure-sensitive adhesive sheet in the pressure-sensitive adhesive strength increasing process is not particularly limited, taking into consideration workability, economy, heat resistance of the base material layer and adherend that can be included in the pressure-sensitive 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. Moreover, the said heating temperature can be 40 degreeC or more, 50 degreeC or more, or 60 degreeC or more, for example, may be 80 degreeC or more, and is good also as 100 degreeC or more. With a higher heating temperature, the adhesive force can be increased by a shorter processing time. 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. Or you may perform heat processing for a longer period (for example, 2 hours or more, 5 hours or more, etc.) as long as remarkable heat deterioration does not arise in an adhesive sheet or a to-be-adhered body. Note that the heat treatment may be performed at once or may be performed in a plurality of times.

  The pressure-sensitive adhesive sheet used in the sticking step may include only one region (first region) that becomes a pressure-sensitive adhesive piece constituting the laminated body in one pressure-sensitive adhesive sheet. For example, as shown in FIG. Two first regions separated from each other may be included, or three or more first regions may be included. When one adhesive sheet includes a plurality of first regions, the shapes 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 that is peeled and removed in the partial removal step, for example, as shown in FIG. Two or more or three or more may be included. When one adhesive sheet includes a plurality of second regions, the shapes of these second regions may be the same or different.

  In the laminated body manufacturing method which concerns on some aspects, what contains multiple units corresponding to the laminated body manufactured by this method can be used as an adhesive sheet and a to-be-adhered body used for a sticking process. This 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 said division | segmentation process can be performed at arbitrary time after performing a sticking process. For example, the cutting process can be performed on a plurality of units collectively by performing the dividing process after at least the cutting process. The manufacturing method disclosed here can be implemented, for example, in such a manner that the dividing step is included between (a) the cutting step and the partial removal step. In the production method including the adhesive strength increasing step after the partial removing step, the dividing step is included, for example, between (b) the partial removing step and the adhesive strength increasing step or (c) after the adhesive strength increasing step. May be implemented. One or more of the above aspects (a) to (c) may be combined. In addition, the said aspect (a) can be preferably implemented using an adhesive sheet provided with the adhesive layer (2) mentioned later, for example. The said aspect (b) and the said aspect (c) can be preferably implemented using an adhesive sheet provided with the adhesive layer (1) or adhesive layer (2) mentioned later, for example.

<< Manufacturing equipment >>
For example, as shown in FIG. 5, the laminated body manufacturing method disclosed herein includes an attaching mechanism 51 for attaching the adhesive sheet 20 to the adherend 10, and a first region 21 and a second region 22 of the adhesive sheet 20. Laminate manufacturing apparatus 50 provided with a cutting mechanism 52 for cutting 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.

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

In addition, the laminated body manufacturing apparatus which can be used for implementation of the laminated body manufacturing method of the aspect including an adhesive force raise process is an adhesive force raise which is not illustrated as a mechanism which gives the irritation | stimulation which raises the adhesive force, for example A mechanism may further be included. The adhesive strength increasing mechanism is configured to perform the adhesive strength increasing step in any of the methods disclosed herein by providing a stimulus that can increase the adhesive strength of the adhesive sheet to the adhesive sheet. ing. The adhesion increasing mechanism includes, for example, one or more of UV irradiation means (UV irradiation lamp, optical path adjustment mirror, etc.), heating means (warm air heater, infrared heater, electric heater, etc.), press means, etc. obtain.
Moreover, the manufacturing apparatus used for the laminated body manufacturing method of the aspect containing a division | segmentation process may further contain the division mechanism which is not shown in figure. The dividing mechanism may be configured so that the dividing step can be performed using a known dividing means such as cutting with a Thomson blade, a pinnacle blade, a rotary blade, a knife, or the like, or laser cutting, water jet cutting, blade cutting or the like. it can.

<< Adhesive sheet >>
Hereinafter, some examples of the pressure-sensitive adhesive sheet that can be preferably employed for carrying out the laminate manufacturing method disclosed herein will be described, but the scope of the present invention is not intended to be limited.

  The laminated body manufacturing method disclosed herein can be preferably implemented 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 structure 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, and thus the second region is easily peeled off from the adherend in the partial removal step.

<Base material layer>
As the substrate layer, various film substrates can be preferably used. 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 has a structure in which a porous layer and a non-porous layer are laminated. Wood may be used. In some embodiments, as the above-mentioned film base material, it is possible to preferably use a film containing a resin film that can maintain its shape independently (independent or independent) as a base film. Here, the “resin film” means a resin film having a non-porous structure and typically containing substantially no 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 having 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), polyamideimide (PAI), and polyetheretherketone (PEEK). ), Polyethersulfone (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene (PTFE) and other fluororesins, acrylic resins Resins such as polyacrylate, polystyrene, polyvinyl chloride, and polyvinylidene chloride can be used.

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

  In the resin film, a light stabilizer, an antioxidant, an antistatic agent, a colorant (dye, pigment, etc.), a filler, a slip agent, an antiblocking agent and the like are known as long as the effect of the present invention is not significantly hindered. These additives can be blended as necessary.

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

  The said base material layer may be comprised substantially from such a base film. Alternatively, the base material 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 and an antireflection layer), a printing layer and a laminate layer for imparting a desired appearance to the base material layer, an antistatic layer, an undercoat layer, and a release layer. And a surface treatment layer such as a layer.

  On the surface of the base material layer on which the pressure-sensitive adhesive layer is laminated, an undercoat layer by applying a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, or a primer (primer) as necessary. Conventionally known surface treatments such as formation of may be performed. Such a surface treatment may be a treatment for improving the anchoring property of the pressure-sensitive adhesive layer to the base material layer. The composition of the primer used for forming 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, preferably about 0.1 μm to 1 μm. Examples of other treatments that can be applied to the base material layer as needed 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 above-mentioned 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 or the like known in the field of pressure-sensitive adhesives at room temperature. One or more of various polymers exhibiting elasticity may be included as a base polymer (a main component of the polymer component, that is, a component occupying more than 50% by weight). Among these, acrylic pressure-sensitive adhesives and rubber-based 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 adhesives. The 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 this specification, an acrylic monomer refers to a monomer having at least one (meth) acryloyl group in one molecule. Moreover, the said (meth) acryloyl group is the meaning which points out an acryloyl group and a methacryloyl group comprehensively.

  Some examples of the pressure-sensitive adhesive layer that can be preferably used in the production method disclosed herein include (1) a pressure-sensitive adhesive layer containing a base polymer and a siloxane structure-containing polymer (hereinafter 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 from a photocurable composition containing a base polymer and a photocuring 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.

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

(Base polymer A)
As the base polymer A (hereinafter sometimes abbreviated as “polymer A”) of the pressure-sensitive adhesive layer (1), an acrylic polymer can be preferably used. 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 polymer A and polymer B means that the adhesiveness of polymer B in the adhesive layer is improved and the low adhesion in the partial removal process and the strong adhesiveness after the adhesive strength increasing treatment (for example, heat treatment) are achieved. This is preferable because it can contribute to the realization of the pressure-sensitive adhesive layer (1). It is preferable that 50% by weight or more of the pressure-sensitive adhesive layer (1) is an acrylic polymer.

As the acrylic polymer, for example, a polymer in which 40% by weight or more of the total amount of monomer components constituting the acrylic polymer is a (meth) acrylic acid alkyl ester can be preferably used. As the (meth) acrylic acid alkyl ester, those having a linear or branched alkyl group having 1 to 20 carbon atoms (that is, C _1-20 ) at the ester terminal can be preferably used. Since it is easy to balance the characteristics, the proportion of the (meth) acrylic acid C _1-20 alkyl ester in the total amount of the constituent monomer components of the acrylic polymer may be, for example, 50% by weight or more, or 55% by weight or more. 60 wt% or more. For the same reason, the proportion of the (meth) acrylic acid C _1-20 alkyl ester in the total amount of the 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 the (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 the (meth) acrylic acid C _1-20 alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, 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, (me T) undecyl acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotridodecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, Examples include heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.

Among these, at least (meth) acrylic acid C _1-18 alkyl ester is preferably used, and at least (meth) acrylic acid C _1-14 alkyl ester is more preferably used. In some embodiments, the constituent monomer component of the acrylic polymer is selected from (meth) acrylic acid C _4-12 alkyl esters (preferably acrylic acid C _4-10 alkyl esters, such as acrylic acid C _6-10 alkyl esters). May be included. For example, an acrylic polymer containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) is preferred, and an acrylic polymer containing at least 2EHA is 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 (meth) acrylic acid alkyl ester as the main component and, if necessary, other monomer (copolymerizable monomer) copolymerizable with (meth) acrylic acid alkyl ester. You may go out. As the copolymerizable monomer, a monomer having a polar group (for example, carboxy group, hydroxy group, etc.) can be preferably used. A monomer having a polar group can serve to introduce a crosslinking point into the acrylic polymer or to increase the cohesive strength of the acrylic polymer. A copolymerizable monomer can be used individually by 1 type or in combination of 2 or more types.

Non-limiting specific examples of the copolymerizable monomer include the following.
Carboxy group-containing monomer: 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) Monomers having a hydroxy group and an amide group, such as hydroxyalkyl (meth) acrylates such as acrylate; N- (2-hydroxyethyl) acrylamide (HEAA), and the like.
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-morpholinedione, N-acryloylmorpholine, N-vinylcarboxylic acid amides 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, phosphate group-containing monomers, acid anhydride group-containing monomers, and the like.

  When such a copolymerizable monomer is used, the amount used is not particularly limited, but it is usually appropriate to be 0.01% by weight or more of the total amount of monomer components. From the viewpoint of better exhibiting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more of the total amount of the monomer components, or 1% by weight or more. The amount of the copolymerizable monomer used can be 50% by weight or less, preferably 40% by weight or less, based on the total amount of the monomer components. Thereby, it can prevent that the cohesion force of an adhesive becomes high too much and can improve the tuck feeling in normal temperature (25 degreeC).

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

  By using N-vinyl cyclic amide, the cohesive force and polarity of the pressure-sensitive adhesive are adjusted, and the adhesive strength after heating (hereinafter, also referred to as “post-heating adhesive strength”) is improved as a stimulus for increasing the adhesive strength. Can be. Specific examples of the N-vinyl cyclic amide include those having the corresponding structure among the nitrogen-containing monomers described above. 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 is 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 amount of the constituent monomer components of the acrylic polymer. Is appropriate. In some embodiments, the amount of N-vinyl cyclic amide used may be 1% by weight or more of the total amount of the monomer components, 5% by weight or more, 8% by weight or more, or 10% by weight or more. It is good also as 12 weight% or more. Further, from the viewpoint of improving tackiness at room temperature (25 ° C.) and improving flexibility at low temperatures, the amount of N-vinyl cyclic amide used is usually 40% by weight or less of the total amount of the monomer components. , 30% by weight or less, 25 parts by weight or less, 20% by weight or less, or 18% by weight or less.

  By using a hydroxyl group-containing monomer, the cohesive force and polarity of the pressure-sensitive adhesive can be adjusted, and the pressure-sensitive adhesive force after heating can be improved. Further, the hydroxyl group-containing monomer can provide a reaction point with a cross-linking agent (for example, an isocyanate-based cross-linking agent) described later, and can increase the cohesive force of the pressure-sensitive adhesive by a cross-linking reaction. Preferable 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 used is not particularly limited, but is 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 amount of the 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 room temperature (25 ° C.) and improving flexibility at low temperature, it is appropriate that the amount of the hydroxyl group-containing monomer is usually 40% by weight or less of the total amount of the monomer components. % Or less, 20% or less, 10% or less, or 5% or less.

  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 based on the total amount of the constituent monomer components of the acrylic polymer, may be 1% by weight or more, and may be 5% by weight. It may be 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more. The total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer can be, for example, 50% by weight or less, and preferably 40% by weight or less, based on the total amount of the monomer components.

In an embodiment in which N-vinyl cyclic amide and a hydroxyl group-containing monomer are used in combination, the relationship (weight basis) between the amount of use of N-vinyl cyclic amide (W _N ) and the amount of hydroxyl group-containing monomer (W _OH ) is particularly limited. Not. W _N / W _OH may be, for example, 0.01 or more, usually 0.05 or more, 0.1 or more, 0.2 or more, 0.5 or more, 0 .7 or more may be used. W _N / W _OH may be, for example, 100 or less, usually 20 or less, 10 or less, 5 or less, 2 or less, or 1.5 or less. 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. The pressure-sensitive adhesive containing the polymer A having a Tg of less than 0 ° C. exhibits an appropriate fluidity (for example, the mobility of the polymer chain contained in the pressure-sensitive adhesive). Is easy to raise. In some embodiments, the Tg of polymer A can be, for example, less than −30 ° C., less than −40 ° C., less than −50 ° C., or less than −60 ° C. The lower limit of Tg of polymer A is not particularly limited. From the viewpoint of easy material availability and improvement in cohesive strength of the pressure-sensitive adhesive layer, usually, a polymer A having a Tg of −80 ° C. or higher can be suitably used.

In this specification, the Tg of a polymer refers to a Tg obtained from the formula of Fox based on the nominal value described in literatures, catalogs, or the like, or the composition of monomer components used in the preparation of the polymer. The formula of Fox is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1 / Tg = Σ (Wi / Tgi)
In the above Fox formula, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio based on weight), and Tgi is the homopolymer of monomer i. Represents the glass transition temperature (unit: K). When the polymer of interest related to the identification of Tg is a homopolymer, the Tg of the homopolymer and the Tg of the polymer of interest coincide.

  As the glass transition temperature of the homopolymer used for the calculation of Tg, the values described in known materials are used. Specifically, the figures are listed in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989). The highest value is adopted for the monomers whose values are listed in the Polymer Handbook.

  Although not particularly limited, it is appropriate that the weight average molecular weight (Mw) of the polymer A is usually about 50,000 or more. From the viewpoint of obtaining a pressure-sensitive adhesive exhibiting better cohesiveness, for example, 100,000 It may be above, 200,000 or more, 300,000 or more, 500,000 or more, or 700,000 or more. In addition, it is appropriate that the Mw of the polymer A is usually about 5 million or less. Such a polymer A of Mw is suitable for realizing a pressure-sensitive adhesive sheet having a high adhesive force increase ratio because it easily forms a pressure-sensitive adhesive exhibiting appropriate fluidity (polymer chain mobility). In some embodiments, the Mw of 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 in terms of polystyrene by gel permeation chromatography (GPC). More specifically, Mw can be measured according to the methods and conditions described in the examples described later.

  The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, photopolymerization method, 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 And system initiators. Non-limiting examples of photoinitiators include benzoin ether photoinitiators, acetophenone photoinitiators, α-ketol photoinitiators, aromatic sulfonyl chloride photoinitiators, photoactive oxime photoinitiators, Examples include benzoin photoinitiators, benzyl photoinitiators, benzophenone photoinitiators, ketal photoinitiators, thioxanthone photoinitiators, and acylphosphine oxide photoinitiators. An initiator can be used individually by 1 type or in combination of 2 or more types.

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

  In some embodiments, the acrylic polymer is a partial polymer (acrylic polymer) obtained by polymerizing a part of the monomer component by irradiating the mixture of the monomer component with an initiator as described above with ultraviolet (UV) irradiation. In the form of a syrup), it can be included in an adhesive composition for forming an adhesive layer. A pressure-sensitive adhesive composition containing such an acrylic polymer syrup can be applied to a predetermined substrate and irradiated with UV to complete the polymerization. That is, the acrylic polymer syrup can be grasped as a precursor of the acrylic polymer. The pressure-sensitive adhesive layer (1) can be formed using, for example, a pressure-sensitive adhesive composition containing such an acrylic polymer syrup and 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 an adhesive strength increase retarder that contributes to suppression of initial adhesive strength and improvement of the adhesive strength increase ratio due to the low polarity and mobility 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 the uneven distribution of polymer B on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet before use (before sticking to the adherend) due to the low polarity derived from the structure, and light peeling at the initial stage of bonding Expresses low viscosity. As the monomer S1, a monomer having a polymerizable reactive group at one end can be preferably used. According to 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 a low initial adhesive force and a high adhesive force 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 a single terminal reactive silicone oil made by Shin-Etsu Chemical Co., Ltd. Monomer S1 can be used individually by 1 type or in combination of 2 or more types.

Here, R ³ in the 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 more 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 the monomer S1 is less than 700 g / mol, the initial adhesive force may not be sufficiently suppressed. When the functional group equivalent of the monomer S1 is 15000 g / mol or more, the increase in adhesive strength may be insufficient. When the functional group equivalent of the monomer S1 is within the above range, it is easy to adjust the compatibility (for example, compatibility with the polymer A) and mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low-tackiness and lamination It becomes easy to realize a pressure-sensitive adhesive sheet that achieves a high level of strong adhesiveness during body use.

Here, “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded per functional group. The title unit g / mol is converted to 1 mol of functional group. The functional group equivalent of the monomer S1 can be calculated from the spectral intensity of ¹ H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. Calculation of the functional group equivalent (g / mol) of the monomer S1 based on the spectrum intensity of ¹ H-NMR is based on a general structural analysis method related to ¹ H-NMR spectrum analysis, and if necessary, Patent No. 5951153. This can be done with reference to the description in the publication.

In addition, when using 2 or more types of monomers from which a functional group equivalent differs as the monomer S1, an arithmetic average value can be used as a functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n types of monomers having different functional group equivalents (monomer S1 ₁ , monomer S1 ₂ ... Monomer S1 _n ) 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 Functional group equivalent × monomer S1 _n blending amount) / (monomer S1 ₁ blending amount + monomer S1 ₂ blending amount +... + Monomer S1 _n blending amount)

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

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

Examples of (meth) acrylic monomers include (meth) acrylic acid alkyl esters. For example, one or more of the monomers exemplified above as the (meth) acrylic acid alkyl ester 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 (meth) acrylic acid C _4-10 alkyl ester, such as (meth) acrylic acid C _6-10 alkyl ester). At least one kind may be contained as a monomer unit. In some other embodiments, polymer B contains at least one methacrylic acid C _1-18 alkyl ester (preferably methacrylic acid C _1-14 alkyl ester, eg, methacrylic acid C _1-10 alkyl ester) as a monomer unit. Can do. The monomer unit constituting the polymer B can include, for example, one or more selected from MMA, BMA, and 2EHMA.

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

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

  Other examples of the monomer that can be included together with the monomer S1 as the monomer unit constituting the polymer B include various copolymerizable monomers exemplified above as the monomer that can be used when the polymer A is an acrylic polymer.

  In some embodiments, the monomer unit common to the monomer unit contained in the polymer B is also contained in the polymer A, whereby the mobility of the polymer B in the pressure-sensitive adhesive layer can be improved and the ratio of increase in the adhesive force can be improved. . The common monomer unit is effectively a component occupying 5% by weight or more of all monomer units constituting the polymer B, and is 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 a component 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 all the monomer units constituting the polymer A increases, the effect of improving the compatibility tends to be exhibited better. In consideration of balance with other characteristics, the ratio of the common monomer unit to all the 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 include MMA, BMA, 2EHMA, methyl acrylate (MA), BA, 2EHA, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl. (Meth) acrylate etc. are mentioned.

  The Mw of the polymer B is not particularly limited. The Mw of the polymer B may be 1000 or more, for example, or 5000 or more. From some viewpoints, the Mw of the polymer B may be, for example, 10,000 or more, 12000 or more, 15000 or more, 17000 or more, or 20000 or more from the viewpoint of increasing the adhesive strength increase property by heating. . Further, the Mw of the polymer B may be, for example, 500000 or less, or 350,000 or less. In view 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, 100,000 or less, 70,000 or less, or 50,000 or less, It may be less than 50000, less than 40000, less than 35000, 30000 or less, 28000 or less, or 25000 or less. When the Mw of the polymer B is within the range of any one of the upper limit value and the lower limit value described above, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, It becomes easy to achieve a high level of strong adhesiveness when using a laminate.

  The polymer B can be prepared, for example, by polymerizing the above-described monomers by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.

  A chain transfer agent can be used to adjust the molecular weight of the 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; thioglycolic acid; methyl thioglycolate , Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, Thioglycolates such as ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate; α- Methylstyrene dimer; and the like.

  The amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0 to 100 parts by weight of the monomer. It is appropriate that the content be 2 to 10 parts by weight. Thus, the polymer B of a suitable molecular weight can be obtained by adjusting the usage-amount of a chain transfer agent. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types.

  Although it does not specifically limit, the usage-amount of the polymer B can be 0.1 weight part or more with respect to the usage-amount of the polymer A 100 weight part, for example, 0.3 from a viewpoint of obtaining a higher effect. Part by weight or more, 0.4 part by weight or more, 0.5 part by weight or more, 1 part by weight or more, or 2 parts by weight or more may be used. From the viewpoint of avoiding an excessive decrease in cohesive force, the amount of polymer B used relative to 100 parts by weight of polymer A may be, for example, 75 parts by weight or less, 50 parts by weight or less, 20 parts by weight or less, 10 It may be up to 8 parts by weight, or up to 5 parts by weight.

  The pressure-sensitive adhesive layer may contain a polymer (arbitrary polymer) other than the polymer A and the polymer B as necessary, as long as the effect obtained by the technique disclosed herein is not significantly impaired. It is appropriate that the amount of such optional polymer used is usually 20% by weight or less of the total 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 of the total polymer component, and may be 1% by weight or less. The pressure-sensitive adhesive layer may contain substantially no polymer other than polymer A and polymer B.

(Crosslinking agent)
A cross-linking agent may be used in the pressure-sensitive adhesive layer as necessary for the purpose of adjusting cohesion. As the crosslinking agent, a crosslinking agent known in the field of pressure-sensitive adhesives can be used. For example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, a metal chelate Examples thereof include a system cross-linking agent. In particular, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent are preferable. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types. The technique disclosed herein can be preferably implemented in an embodiment using at least an isocyanate-based crosslinking agent as the crosslinking agent.

  Examples of isocyanate-based 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 diene Aromatic isocyanates such as isocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / tolylene diisocyanate trimer adduct (for example, “Coronate L” manufactured by Tosoh), trimethylolpropane / hexamethylene Diisocyanate trimer adduct (for example, “Coronate HL” manufactured by Tosoh), xylylene diisocyanate trimethylolpropane adduct (for example, “Taito” manufactured by Mitsui Chemicals, Inc.) Sulfonates D110N ", isocyanurate of hexamethylene diisocyanate (e.g., manufactured by Tosoh" Coronate HX ") isocyanate adducts of the like.

  Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resins, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Mention glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc. Can do.

  The amount used in the case of using the crosslinking agent is not particularly limited, and can be, for example, an amount exceeding 0 part by weight with respect to 100 parts by weight of the polymer A. In some embodiments, the amount of crosslinking agent used relative to 100 parts by weight of polymer A may be, for example, 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight. Part or more, 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more. Higher cohesion tends to be obtained by increasing the amount of the crosslinking agent used. On the other hand, from the viewpoint of avoiding a decrease in tack due to excessive cohesive strength improvement, the amount of the crosslinking agent used relative to 100 parts by weight of the polymer A is usually suitably 15 parts by weight or less, and may be 10 parts by weight or less. It may be 5 parts by weight or less. The fact that the amount of the crosslinking agent used is not too large can be advantageous from the viewpoint of better expressing the effect of using the polymer B by utilizing the fluidity of the pressure-sensitive adhesive.

  In order to advance the crosslinking reaction more effectively, a crosslinking catalyst may be used. Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, nurse ferric iron, butyl tin oxide, and dioctyl tin dilaurate. Of these, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferred. The amount of the crosslinking catalyst used is not particularly limited, and can be, for example, about 0.0001 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 may be used for the pressure-sensitive adhesive layer as necessary. The polyfunctional monomer can be used for the purpose of adjusting the cohesive force by being used in place of the crosslinking agent as described above or in combination with the crosslinking agent. For example, in a pressure-sensitive adhesive layer formed from a photocurable pressure-sensitive adhesive composition, a polyfunctional monomer can be preferably used.
Examples of the multifunctional monomer 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, trimethylolpropane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, allyl (meth) acrylate, vinyl Le (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl diol (meth) acrylate, hexyl di (meth) acrylate. Among these, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

  The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, and the like, but it is usually appropriate to be in the range of about 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polymer A. . In some embodiments, the amount of the polyfunctional 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. Higher cohesion tends to be obtained by increasing the amount of the polyfunctional monomer used. On the other hand, from the viewpoint of avoiding a decrease in tack due to excessive cohesion, the amount of the polyfunctional monomer used may be 2.0 parts by weight or less with respect to 100 parts by weight of the polymer A, and even 1.0 part by weight or less. It may be 0.5 parts by weight or less. The fact that the amount of the polyfunctional monomer used is not too large can be advantageous from the viewpoint of better expressing the effect of using the polymer B by utilizing the fluidity of the pressure-sensitive adhesive.

(Tackifying resin)
The pressure-sensitive adhesive layer can contain a tackifier resin as necessary. The tackifying resin is not particularly limited. For example, rosin tackifying resin, terpene tackifying resin, phenol tackifying resin, hydrocarbon tackifying resin, ketone tackifying resin, polyamide tackifying resin, Examples thereof include an epoxy tackifying resin and an elastomer tackifying resin. Tackifying resin can be used individually by 1 type or in combination of 2 or more types.

  In the embodiment in which the tackifier resin is included in the pressure-sensitive adhesive layer, the content of the tackifier resin is not particularly limited, and can be set so that appropriate tackiness performance is exhibited depending on the purpose and application. The content of the tackifier resin relative to 100 parts by weight of the polymer A (when two or more tackifier resins are included, the total amount thereof) can be, for example, about 5 to 500 parts by weight. In addition, the technique disclosed here is an embodiment in which the content of the tackifier resin with respect 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 adhesive layer is substantially tackified. An embodiment that does not contain a resin can also be preferably implemented.

  As the tackifier 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. According to the tackifier resin having a softening point equal to or higher than the lower limit value described above, the initial low tackiness and the strong tackiness when using the laminate tend to be effectively improved. The upper limit of the softening point is not particularly limited, and can be, for example, about 200 ° C. or lower (typically 180 ° C. or lower). The softening point of the tackifying resin can be measured based on the softening point test method (ring ball method) defined in JIS K2207.

(Formation of adhesive layer)
The pressure-sensitive adhesive layer (1) can be a cured layer of the pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive layer (1) can be formed by appropriately applying a curing treatment after applying a water-dispersed, solvent-type, photo-curable, or hot-melt type pressure-sensitive adhesive composition to an appropriate surface. . When two or more kinds of curing treatments (drying, crosslinking, polymerization, cooling, etc.) are performed, these can be performed simultaneously or over a plurality of stages. In an adhesive composition using a partially polymerized monomer component (acrylic polymer syrup), a final copolymerization reaction is typically performed as the curing treatment. That is, the partial polymer is subjected to a further copolymerization reaction to form a complete polymer. For example, if it is a photocurable adhesive composition, light irradiation is implemented. If necessary, curing treatment such as cross-linking and drying may be performed. For example, when it is necessary to dry with a photocurable adhesive composition, it is good to perform photocuring after drying. In the pressure-sensitive adhesive composition using a completely polymerized product, typically, as the curing treatment, treatments such as drying (heat drying) and crosslinking are performed as necessary.

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

<Adhesive layer formed from photocurable composition containing base polymer P and photocuring agent>
The pressure-sensitive adhesive layer (2) contains the base polymer P and a photocuring agent, and exhibits a property that the pressure-sensitive adhesive force is improved by being cured by irradiation with actinic rays (for example, UV). Utilizing such properties, for example, the adhesive strength before photocuring is configured to be 2 N / 25 mm or less, and the pasting step, the cutting step and the partial removing step are performed before the photocuring, followed by photocuring and adhesion. In a mode of increasing the force (typically, increasing to 5 N / 25 mm or more), it can be suitably used for the execution of the laminate manufacturing method disclosed herein. From the viewpoint of increasing the efficiency of curing by actinic ray irradiation, the pressure-sensitive adhesive composition (photocurable composition) constituting the pressure-sensitive adhesive layer (2) preferably contains a photoinitiator. From the viewpoint of suppressing the phenomenon that the adhesive remains on the adherend when the adhesive layer in the second region is peeled and removed in the partial removal process, that is, the adhesive remaining phenomenon before the photocuring is hardened. The base polymer P is preferably introduced with a crosslinked structure.

(Base polymer P)
As the base polymer P (hereinafter sometimes abbreviated as “polymer P”) of the pressure-sensitive adhesive layer (2), an acrylic polymer can be preferably used 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, a polymer in which 40% by weight or more of the total amount of the constituent monomer components is the same (meth) acrylic acid alkyl ester as that of the polymer A described above can be preferably used.

  The acrylic polymer preferably contains a monomer component having a crosslinkable functional group as a copolymerization component. Examples of the monomer having a crosslinkable functional group include a hydroxy group-containing monomer and a carboxy group-containing monomer. Examples of the hydroxy group-containing monomer and the carboxy group-containing monomer include the same monomers as those exemplified as the constituent monomer component of the polymer A contained in the pressure-sensitive adhesive layer (1). Especially, it is preferable to contain a hydroxyl group containing monomer. The hydroxy group or carboxy group of the polymer P becomes a reaction point with a cross-linking agent described later. By introducing a cross-linked structure into the polymer P, the cohesive force is improved, the adhesiveness of the pressure-sensitive adhesive layer (2) is improved, and the fluidity of the pressure-sensitive adhesive is lowered. There is a tendency for adhesive residue to be reduced.

  In the acrylic polymer, the total amount of the hydroxy group-containing monomer and the carboxy group-containing monomer with respect to the total amount of the constituent monomer components is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and more preferably 5 to 20%. More preferably, it is% by weight. 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 structural 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 the constituent monomer components is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and further preferably 5 to 20% by weight. The acrylic polymer preferably contains N-vinylpyrrolidone in the above range as a nitrogen-containing monomer.

  When the acrylic polymer contains both a hydroxy group-containing monomer and a nitrogen-containing monomer as monomer components, the cohesive force and transparency of the pressure-sensitive adhesive tend to be improved. In the acrylic polymer, the total amount of the hydroxy group-containing monomer and the nitrogen-containing monomer with respect to the total amount of the constituent monomer components is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and 15 to 35% by weight. More preferably.

  Acrylic polymers are monomer components other than those described above, for example, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy group-containing monomers, vinyl ether monomers, sulfo group-containing monomers, phosphate group-containing monomers, acid anhydride groups. A contained monomer or the like may be contained.

  In the acrylic polymer, the content of the monomer having a Tg of 40 ° C. or higher in the homopolymer is preferably 5 to 50% by weight, preferably 10 to 40% by weight, based on the total amount of the constituent monomer components of the acrylic polymer. It is more preferable. From the viewpoint of suppressing adhesive residue in the partial removal step, the constituent monomer component of the polymer P preferably includes a monomer component having a Tg of homopolymer of 80 ° C. or higher, and a monomer component having a Tg of homopolymer of 100 ° C. or higher. More preferably. In the acrylic polymer, the content of the monomer having a Tg of 100 ° C. or higher with respect to the total amount of the constituent monomer components is preferably 0.1% by weight or more, 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 MMA content is preferably in the above range. In addition, the suitable range of Tg of the acrylic polymer used as the polymer P can be the same as the suitable Tg of the polymer A described above.

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

  The adhesive force of the pressure-sensitive adhesive layer before photocuring is easily influenced by the constituent components and molecular weight of the polymer P. From the viewpoint of achieving both moderate adhesiveness and suppression of adhesive residue in the partial removal step, 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 500,000. ~ 2 million is more preferred. In addition, when a crosslinked structure is introduced into the polymer P, the molecular weight of the polymer P refers to the molecular weight before the introduction of the crosslinked structure.

(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 into the polymer P. For example, a crosslinking structure is introduced by adding a crosslinking agent to the solution after polymerizing the polymer P and heating as necessary. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents react with a functional group such as a hydroxy group 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.

  What is necessary is just to adjust the usage-amount of a crosslinking agent suitably according to a composition, molecular weight, etc. of the polymer P. FIG. 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, relative to 100 parts by weight of the polymer P. More preferably, it is 1-4 weight part. In order to promote the formation of a crosslinked structure, a crosslinking catalyst may be used in the same manner as the pressure-sensitive adhesive layer (1).

(Photocuring agent)
The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer (2) is configured to exhibit photocurability by containing a photocuring agent in addition to the polymer P. The pressure-sensitive adhesive layer (2) exhibits a property that, after being bonded to an adherend, by irradiating with an actinic ray as a stimulus for increasing the adhesive strength, it is photocured to improve the adhesive strength.

  As the photocuring agent, a photocurable monomer or a photocurable oligomer is used. As the photocuring agent, a compound having two or more ethylenically unsaturated bonds in one molecule is preferable. In addition, the photocuring agent is preferably a compound showing compatibility with the polymer P. In view of moderate compatibility with the polymer P, the photocuring agent is preferably liquid at room temperature. When the photocuring agent is compatible with the polymer P and is uniformly dispersed in the composition, a contact area with the adherend can be secured, and a highly transparent pressure-sensitive adhesive layer (2) can be formed.

  The compatibility between the polymer P and the photocuring agent is mainly influenced by the structure of the compound. The structure and compatibility of the compound can be evaluated by, for example, the Hansen solubility parameter, and the compatibility tends to increase as the difference in the solubility parameter between the polymer P and the photocuring agent decreases.

  Since the compatibility with the acrylic polymer is high, it is preferable to use a polyfunctional (meth) acrylate as a photocuring agent. Polyfunctional (meth) acrylates include 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 isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol La (meth) acrylate, pentaerythrole tetra (meth) acrylate, dipentaerystol poly (meth) acrylate, dipentaerythrole hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate , Urethane (meth) acrylate, epoxy (meth) acrylate, butadiene (meth) acrylate, isoprene (meth) acrylate, and the like.

  The compatibility between the polymer P and the photocuring agent also depends on the molecular weight of the compound. There exists a tendency for compatibility with the polymer P to become high, so that the molecular weight of a photocurable compound is small. From the viewpoint of compatibility with the polymer P, the molecular weight of the photocuring agent is preferably 1500 or less, and more preferably 1000 or less.

  The type and content of the photocuring agent mainly affect the adhesive strength after photocuring. 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 photocuring agent is larger, the adhesive strength after photocuring tends to increase.

  From the viewpoint of increasing the adhesive strength after photocuring, the functional group equivalent (g / eq) of the photocuring agent is preferably 500 or less, and more preferably 450 or less. On the other hand, when the photocrosslinking density is excessively increased, the viscosity of the pressure-sensitive adhesive may be decreased to decrease the adhesive strength. Therefore, the functional group equivalent of the photocuring agent is preferably 100 or more, more preferably 130 or more, further preferably 150 or more, and particularly preferably 180 or more.

  In the combination of an acrylic polymer and a polyfunctional acrylate photocuring agent, when the functional group equivalent of the photocuring agent is small, the interaction between the polymer P and the photocuring agent is strong, and the adhesive force before photocuring tends to increase. is there. In the technique disclosed herein, the functional group equivalent of the photocuring agent is within the above range from the viewpoint of suppressing the adhesive force before photocuring to an appropriate range and enhancing the removability of the second region in the partial removal step. It is preferable that

  1-50 weight part is preferable with respect to 100 weight part of polymers P, as for content of the photocuring agent in an adhesive composition, 5-40 weight part is more preferable, and 10-35 weight part is further more preferable. A photocurable adhesive layer is obtained by a photocurable compound being contained in an adhesive composition as an uncured (unreacted) monomer or oligomer. In order to include the photocuring agent in the composition in an uncured state, it is preferable to add the photocuring agent to the polymer solution after polymerizing the polymer P.

  When the content of the photocuring agent in the pressure-sensitive adhesive composition increases, the photocuring agent tends to bleed out on the surface of the pressure-sensitive adhesive layer. When a large amount of the photocuring agent bleeds out, the photocuring agent tends to remain on the adherend after removing the second region. On the other hand, by bleeding out a small amount of photocuring agent on the surface, the adhesive strength of the pressure-sensitive adhesive layer to the adherend is suppressed, and both low tackiness before photocuring and strong tackiness after photocuring are compatible. It becomes possible to make it.

(Photoinitiator)
The pressure-sensitive adhesive layer (2) preferably contains a photoinitiator. The photoinitiator generates active species upon irradiation with actinic rays and promotes the curing reaction of the photocuring agent. As the photoinitiator, a photocationic initiator (photoacid generator), a photoradical initiator, a photoanion initiator (photobase generator), or the like is used depending on the type of the photocuring agent. When a polyfunctional acrylate is used as the photocuring agent, it is preferable to use a photoradical initiator. Examples of the photo radical initiator include hydroxy ketones, benzyl dimethyl ketals, amino ketones, acyl phosphine oxides, benzophenones, trichloromethyl group-containing triazine derivatives, and the like. A photoradical generator may be used independently and may be used in mixture of 2 or more types. 0.001-10 weight part is preferable with respect to 100 weight part of whole quantity of an adhesive layer, and, as for content of the photoinitiator in an adhesive layer, 0.01-5 weight part is more preferable.

(Other additives)
In addition to the components exemplified above, the pressure-sensitive adhesive layer is composed of a silane coupling agent, a tackifier, a plasticizer, a softener, a deterioration inhibitor, a filler, a colorant, an ultraviolet absorber, an antioxidant, and a surfactant. Further, additives such as antistatic agents 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 formed by, for example, applying a pressure-sensitive adhesive composition containing the polymer P, a photo-curing agent and other components used as necessary to an appropriate surface, and then removing the solvent by drying as necessary. Can be formed. As a drying method, an appropriate method can be adopted as appropriate. The heat 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, and even more preferably 10 seconds to 10 minutes.

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

(Friction force)
The pressure-sensitive adhesive layer (2) before photocuring has a friction force at a frequency of 5 Hz measured by a tapping mode of a friction force microscope (FFM) from the viewpoint of easily suppressing the adhesive force. It is preferably 2 to 5 times the force. Moreover, when the ratio of the frictional force between the frequency of 0.1 Hz and the frequency of 5 Hz of the pressure-sensitive adhesive layer (2) is in this range, the pressure-sensitive adhesive force tends to be greatly increased compared to that before light-curing.

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

  The frictional force due to nanotribology tends to reflect the adhesion of the surface of the pressure-sensitive adhesive layer to the adherend, and a small frictional force means that the surface of the pressure-sensitive adhesive is close to a liquid and has low stickiness. . When the surface of the pressure-sensitive adhesive layer has viscosity, the frictional force increases and frequency dependency appears in the frictional force measured by FFM. 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 characteristics. 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 higher the viscosity and the higher the adhesion to the adherend. For example, if the base polymer of the adhesive layer and the photocuring agent are not completely compatible, the liquid photocuring agent bleeds out to the surface and adheres to the adhesion interface with the adherend (Weak Boundary Layer). ; WBL) is formed and the liquid property becomes stronger, so that the frictional force and the frequency dependence of the frictional force tend to be reduced.

  By controlling the compatibility between the polymer P and the photocuring agent in the pressure-sensitive adhesive layer (2), a small amount of the photocuring agent may bleed out on the surface of the pressure-sensitive adhesive layer, and WBL may be formed. When the WBL is appropriately formed, the surface (adhesion interface) characteristics change, and the frictional force and the frequency dependence of the frictional force become smaller. Thereby, it becomes easy to suppress the adhesive force before photocuring, and peeling of the 2nd field in the case of performing a partial removal process before the photocuring becomes easy.

  When the frictional force at a frequency of 5 Hz of the pressure-sensitive adhesive layer before photocuring is 5 times or less than the frictional force at a frequency of 0.1 Hz, the pressure-sensitive adhesive layer before photocuring and the adherend are easily peeled off. Tend. From the viewpoint of avoiding bleed-out of the photocuring agent, the frictional force of the pressure-sensitive adhesive layer at a frequency of 5 Hz is preferably at least twice that of the frictional force at a frequency of 0.1 Hz, more preferably at least three times, and more than 3.5 times. Is more preferable.

  From the viewpoint of achieving both appropriate adhesion to the adherend and peelability, the FFM difference signal at a frequency of 5 Hz of the pressure-sensitive adhesive layer before photocuring measured using a cantilever having 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 further more preferable, and 0.2-0.7V is particularly preferable.

  From the viewpoint of increasing the adhesive strength after photocuring, it is preferable that the adhesive layer after photocuring has a frictional force at a frequency of 5 Hz measured by FFM is not less than 5 times the frictional force at a frequency of 0.1 Hz. It is more preferably 5.5 times or more. The FFM difference signal at a frequency of 5 Hz of the adhesive layer after photocuring measured using a cantilever having a spring constant of 40 N / m is preferably 0.1 V or more, more preferably 0.2 V or more, and further 0.3 V or more. preferable. From the viewpoint of improving the adhesive strength, the frictional force of the pressure-sensitive adhesive layer after photocuring is preferably as large as possible. Therefore, although the upper limit of the frictional force is not particularly limited, the FFM differential signal at 5 Hz measured using a cantilever having 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 properties. Is preferred.

  The frictional force of the pressure-sensitive adhesive layer after photocuring at a frequency of 5 Hz is preferably 1.5 times or more, more preferably 2 times or more, and 2.5 times that of the pressure-sensitive adhesive layer before photocuring at a frequency of 5 Hz. The above is more preferable, and 3 times or more is particularly preferable. As the ratio of the frictional force before and after photocuring increases, the rate of increase in adhesive force due to photocuring tends to increase. The frictional force after photocuring is generally 20 times or less, preferably 10 times or less than the frictional force before photocuring.

Note that the friction force at the frequency of 0.1 Hz and 5 Hz of the pressure-sensitive adhesive layer before and after photocuring is FFM mode of a scanning probe microscope (“AFM5300E” manufactured by Hitachi High-Tech Science) under the following conditions. It is measured by performing a frictional measurement with a scanning width of 5 μm in the direction (10 μm scanning in a reciprocating direction) and reading a differential voltage at a position of 3 μm from the left side of the measurement range.
(Measurement condition)
Cantilever: “Tap300E-G” from BudgetSensors (equivalent to a spring constant of 40 N / m)
ADD value: 8.44V, DIF value: 0.4V, FFM value: 0V
Atmosphere: Vacuum, room temperature Scan speed: 0.1 Hz, 1 Hz and 5 Hz

  Examples of actinic rays that can be used for photocuring of the pressure-sensitive adhesive layer (2) include ultraviolet rays (UV), visible light, infrared rays, X-rays, α rays, β rays, and γ rays. UV is preferable as the actinic ray because it is easy to suppress curing of the pressure-sensitive adhesive layer in the storage state and it is easy to cure. What is necessary is just to set the irradiation intensity | strength and irradiation time of actinic light suitably according to a composition, thickness, etc. of an adhesive layer.

  The pressure-sensitive adhesive layer (2) is photocurable, and the timing for increasing the adhesive force by curing can be arbitrarily set. Therefore, after removing the adhesive sheet on the adherend, it is possible to carry out a partial removal process at any time before the adhesive is photocured, so it is possible to respond flexibly to the lead time of the device manufacturing process. It is.

<Structure of adhesive sheet>
The thickness of the pressure-sensitive adhesive sheet used in the production method disclosed herein is not particularly limited, and may be, for example, about 3 μm to 11 mm. From the viewpoint of the handleability of the pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive sheet is usually suitably 5 μm or more, and may be 10 μm or more, or 30 μm or more. 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 can be preferably used from the viewpoint of the workability of peeling the second region in the partial removal step. Further, from the viewpoint of cutting workability in the cutting step and peeling workability of the second region in the partial removal step, the thickness of the pressure-sensitive adhesive sheet may be, for example, 1000 μm or less, 600 μm or less, and 350 μm. Or may be 200 μm or less, or 150 μm or less.

  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 more than 20 μm. By increasing the thickness of the pressure-sensitive adhesive layer, a laminate in which the pressure-sensitive 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, workability in the partial removal process (for example, the first region and the second region) due to blocking between the pressure-sensitive adhesive in the first region and the pressure-sensitive adhesive in the second region. The separability may be reduced. From such a viewpoint, 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 base material layer may be, for example, 5 μm or more, may be 10 μm or more, and 25 μm from the viewpoint of handling of the pressure-sensitive adhesive sheet and prevention of tearing of the second region in the partial removal process. The above may be sufficient, 35 micrometers or more may be sufficient, 50 micrometers or more may be sufficient, and 60 micrometers or more may be sufficient. In some embodiments, from the viewpoint of cutting processability in the cutting step, 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, It may be 150 μm or less, 100 μm or less, or 90 μm or less.

  The pressure-sensitive adhesive sheet used in the production method disclosed herein can be suitably implemented in a mode in which the thickness Ts of the base material layer is larger than the thickness Ta of the pressure-sensitive adhesive layer. That is, Ts / Ta is preferably larger than 1. 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. Ts / Ta may be 50 or less, 20 or less, 10 or less, or 7 or less, for example. By using the pressure-sensitive adhesive sheet having a configuration satisfying any one of the above upper limit values and / or satisfying any one of the above lower limit values, good peeling workability in the partial removal process and finally obtained lamination There is a tendency that the adhesiveness of the adhesive piece to the adherend in the body is balanced with a good balance.

In some embodiments, the pressure-sensitive adhesive sheet used in the sticking step may have an area of, for example, 2500 cm ² or more and a short side length of 50 cm or more. Thus, in the aspect using a large-sized pressure-sensitive adhesive sheet, it is particularly meaningful to employ the production method disclosed herein. By using such an adhesive sheet, for example, one or more effects among the improvement of positional accuracy, the improvement of shape accuracy, the improvement of productivity, etc. tend to be suitably exhibited. In addition, 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 pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet exceeds 2 N / 25 mm. Thus, even if it is a large-sized adhesive sheet, it is easy to peel and remove the second region. According to an 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 an embodiment in which the length of the short side is 60 cm or more, more preferably 70 cm or more, even higher effects can be exhibited.

<Application>
According to the method disclosed herein, it is possible to efficiently produce a laminate in which a pattern made of an adhesive piece is accurately formed on an adherend and the pattern has excellent durability. Taking advantage of such features, the method disclosed herein can be applied to vehicle exterior materials and interior materials, building materials such as building exterior materials and interior materials, window glass, signboards, signs, home appliances, optical products, and electronic products. The present invention can be preferably applied to an application in which a product or a constituent member thereof is an adherend, and such an adherend is partially covered with a pattern of adhesive pieces. The laminate may be the above-described various products or constituent members thereof. The adhesive piece is included in various products as a component of the laminate, so that the adherend included in the laminate, or the product including the laminate and its members are decorated, displayed, protected, reinforced, It can be useful for imparting functions such as impact relaxation, stress concentration relaxation, shape maintenance, shape recovery, and the like. The method disclosed here can be preferably applied to the manufacture of an FPC equipped with a film coverlay, for example.

  Further, in optical members used in optical products and electronic members used in electronic products, advanced integration, miniaturization, lightening, and thinning are progressing, and a plurality of thin optical members having different linear expansion coefficients and thickness / Electronic members can be stacked. By using such a member as an adherend and forming a laminate in which the member is partially covered with an adhesive piece by using the method disclosed herein, the optical member / electronic member has a moderate rigidity. Can be granted. Thereby, in a manufacturing process and / or a product after manufacturing, curling and bending due to stress that can occur between a plurality of members having different linear expansion coefficients and thicknesses can be suppressed.

  Further, in the optical product / electronic product manufacturing process, in the aspect where the thin optical member / electronic member is subjected to shape processing such as cutting processing as described above, the member (adherent) is partially covered with the adhesive piece. By forming a broken laminate, the adhesive piece is used as a reinforcing member, local stress concentration on the optical member / electronic member associated with the processing of the laminate is alleviated, cracks, cracks, laminated members Risk of peeling off can be reduced. Affixing a reinforcing member to an optical member / electronic member can be used to alleviate local stress concentration during conveyance, lamination, rotation, etc. of the member, or to suppress bending or bending due to its own weight. Can be helpful.

  Furthermore, when an adherend is a device such as an optical product or an electronic product that includes a laminate that is partially covered with the pattern of the adhesive piece, when the device falls in a stage where it is used by consumers in the market, Even when unintentional stress is applied, such as when the object is placed under a heavy object or when a flying object collides, the adhesive piece included in the device functions as a reinforcing member. Such stress can be alleviated and durability can be improved.

  The method disclosed herein is preferably used, for example, for manufacturing a laminate in which constituent members of various portable devices (portable devices) are used as adherends and the members are partially covered with a pattern of adhesive pieces. obtain. Here, “carrying” means that it is not enough to be able to carry it alone, but means that the individual (standard adult) has a level of portability that can be carried relatively easily. To do. Examples of mobile devices here include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices, digital cameras, digital video cameras, audio devices (portable music players, IC recorders, etc.), 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 modems, and other portable electronic devices, mechanical watches and pocket watches A watch, flashlight, hand mirror, etc. may be included. Examples of the members constituting the portable electronic device may include an optical film, a display panel, and the like used for an image display device such as a thin layer display such as a liquid crystal display or a film type display. The method disclosed herein can be preferably applied to an application in which various members in automobiles, home electric appliances, and the like are used as adherends, and the members are partially covered with a pattern of adhesive pieces.

  Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to the specific examples. In the following description, “parts” and “%” are based on weight unless otherwise specified.

(Preparation of polymer A1)
In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser, 63 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of N-vinylpyrrolidone (NVP), 9 parts of methyl methacrylate (MMA), 2- After 13 parts of hydroxyethyl acrylate (HEA) and 200 parts of ethyl acetate as a polymerization solvent were added and stirred for 2 hours at 60 ° C. in a nitrogen atmosphere, 0.2 part of AIBN was added as a thermal initiator, and 6 parts at 60 ° C. were added. Reaction was performed for a time to obtain a solution of polymer A1. The 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 the synthesis of polymer A1, except that the composition of the monomer used was changed to 2EHA / HEA = 95/5 (weight ratio). The Mw of this polymer A2 was 900,000.

(Preparation of polymer A3)
A reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a condenser was charged with 96.2 parts of 2EHA, 3.8 parts of HEA, and 150 parts of ethyl acetate as a polymerization solvent, and 2 at 60 ° C. under a nitrogen atmosphere. After stirring for a period of time, 0.2 part of AIBN was added as a thermal initiator and reacted at 60 ° C. for 6 hours to obtain a polymer A3 solution (solid content 40%). The Mw of this polymer A3 was 540,000.

(Preparation of polymer B1)
In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction pipe and a condenser, MMA 40 parts, n-butyl methacrylate (BMA) 20 parts, 2-ethylhexyl methacrylate (2EHMA) 20 parts, and a functional group equivalent of 900 g / mol 9 parts of polyorganosiloxane skeleton-containing methacrylate monomer (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.), polyorganosiloxane skeleton-containing methacrylate monomer (trade name: KF-2012) having a functional group equivalent of 4600 g / mol 11 parts, manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts of ethyl acetate, and 0.6 part of thioglycerol as a chain transfer agent were stirred at 70 ° C. under a nitrogen atmosphere for 1 hour, and then AIBN0 was used as a thermal initiator. .2 parts was added and reacted at 70 ° C. for 3 hours. Was of AIBN introduced, was followed by 5 hours of reaction at 80 ° C.. In this way, a solution of the siloxane structure-containing polymer B1 was obtained. The Mw of this polymer B1 was 20000.

In addition, the weight average molecular weight of each polymer mentioned above measured on the following conditions using the GPC apparatus (the Tosoh company make, HLC-8220GPC), and 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 ℃
·column:
Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
Reference column; TSKgel SuperH-RC (1 piece)
・ Detector: Differential refractometer (RI)

<Production of adhesive sheet>
(Adhesive sheet D1)
In 100 parts of the polymer A1 contained in the solution, 2.5 parts of the polymer B1 and an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, 2.5 parts of Mitsui Chemicals Co., Ltd. was added and mixed uniformly to prepare an adhesive composition C1.
The pressure-sensitive adhesive composition C1 was directly applied to one side of a 75 μm-thick PET film (Toray “Lumoror S10”) that had not been surface-treated, and heated at 110 ° C. for 2 minutes and dried to a thickness of 25 μm. A pressure-sensitive adhesive layer is formed, and a release-treated surface of a release liner (MRQ50T100 manufactured by Mitsubishi Chemical Co., Ltd., a polyester film treated on one side with a silicone-based release agent, thickness 50 μm) is formed on the surface (adhesive surface) of the pressure-sensitive adhesive layer. Laminated and protected. In this way, a pressure-sensitive adhesive sheet D1 having a pressure-sensitive adhesive layer on one surface of a base material 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 with a release liner is obtained. It was.

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

(Adhesive sheet D3)
An isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) is added to the polymer A2 solution based on a solid content of 2.5 parts per 100 parts of the polymer A2 contained in the solution. A pressure-sensitive adhesive composition C3 was prepared by adding parts and mixing uniformly. A pressure-sensitive adhesive sheet D3 having a pressure-sensitive adhesive surface protected with a release liner was obtained in the same manner as the pressure-sensitive adhesive sheet D1, except that the pressure-sensitive adhesive composition C3 was used instead of the pressure-sensitive adhesive composition C1.

(Adhesive sheet D4)
A pressure-sensitive adhesive composition C4 was prepared in the same manner as the pressure-sensitive adhesive composition C1 except that the polymer B1 was not used. A pressure-sensitive adhesive sheet D4 having a pressure-sensitive adhesive surface protected with a release liner was obtained in the same manner as the pressure-sensitive adhesive sheet D1 except that the pressure-sensitive adhesive composition C4 was used in place of the pressure-sensitive adhesive composition C1.

(Adhesive sheet D5)
In 100 parts of the polymer A3 contained in the solution, 2.5 parts of the polymer B1, 2.5 parts of an isocyanate-based crosslinking agent (trade name: Coronate L (trimethylolpropane / tolylene diisocyanate) 3.3 parts of a 75% ethyl acetate solution of a trimer adduct, manufactured by Tosoh Corporation) was added and mixed uniformly to prepare an adhesive composition C5, which was replaced with an adhesive composition C1. Except for using C5, a pressure-sensitive adhesive sheet D5 having a pressure-sensitive adhesive surface protected by a release liner was obtained in the same manner as the pressure-sensitive adhesive sheet D1.

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

Furthermore, the measurement sample prepared from the adhesive sheet D1, D5, in the same manner as in the measurement of the initial adhesion B ₀ crimped to the test piece was allowed to stand 30 minutes under the standard environment, and heated at 80 ° C. 5 minutes . Further, after leaving for 30 minutes in the above standard environment, the peel strength (adhesive strength after heating) [N / 25 mm] was similarly measured under the conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min. .94 N / 25 mm, and 5.45 N / 25 mm for the adhesive sheet D5.
Furthermore, the measurement sample prepared from the adhesive sheet D2, in the same manner as in the measurement of the initial adhesion B ₀ crimped to the test piece was allowed to stand under the standard environment for 30 minutes, using a UniField manufactured by Ushio Inc., Ultraviolet rays having a dominant wavelength of about 365 nm were irradiated so as to obtain a light amount of 2000 mJ / cm ² . Further, after being left for 30 minutes in the above standard environment, the peel strength (adhesive strength 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.

<Manufacture of laminates>
(Production Example 1)
The pressure-sensitive adhesive sheet D1 was cut into a size of 25 mm in width and 100 mm in length to prepare a pressure-sensitive adhesive sheet for producing a laminate. In addition, 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) was prepared as an adherend.
The center of the adherend and the center of the pressure-sensitive adhesive sheet were aligned, and the pressure-sensitive adhesive sheet was attached to the adherend with a hand roller (sticking step).
A cut process was performed after the pressure-sensitive adhesive sheet was attached to the adherend and before the following partial removal process. A second region having a width of 2 mm and a length of 100 mm extending linearly from one end to the other end in the longitudinal direction of the pressure-sensitive adhesive sheet is set at the width center of the pressure-sensitive adhesive sheet in the obtained pressure-sensitive adhesive sheet / adhesive laminate, By irradiating a laser from the adhesive sheet surface side along the boundary (two straight lines) between the second region and the first region on both sides thereof, a cutting process for cutting only the adhesive sheet D1 was performed. The cutting process was performed under the following conditions using a laser cutting device “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 step was performed. Specifically, one end of the second region is peeled off from the adherend, and is gripped by a chuck of a tensile tester, and pulled in the longitudinal direction of the pressure-sensitive adhesive sheet at a peeling angle of 180 degrees and a tensile speed of 300 mm / min. The slit-shaped second region was peeled and removed from the adherend.
Next, the above-described heating (80 ° C., 5 minutes) is performed as an adhesive force increase stimulus (adhesive force increasing step), and the target laminate, that is, the adherend is covered with the patterned adhesive sheet. A laminate having the structure described above was produced. Table 1 shows the value of the adhesive strength after 12 hours of room temperature of the adhesive sheet D1 as the adhesive strength during the partial removal step of Production Example 1, and the value of the adhesive strength after heating of the adhesive sheet D1 as the adhesive strength of the laminate. is doing.

(Production Example 2)
Except for using the adhesive sheet D2 in place of the adhesive sheet D1 and changing the stimulus applied in the adhesive strength increasing step from heating to the above-mentioned UV irradiation (main wavelength: about 365 nm, light amount: 2000 mJ / cm ² ), A laminate was produced in the same procedure as in Production Example 1. Table 1 shows the value of the adhesive strength after 12 hours of room temperature of the adhesive sheet D2 as the adhesive strength during the partial removal step of Production Example 2, and the value of the adhesive strength after UV irradiation of the adhesive sheet D2 as the adhesive strength of the laminate. It is described.

(Production Examples 3 and 4)
Each of the pressure-sensitive adhesive sheets shown in Table 1 is used, and after the cutting step, neither heating nor UV irradiation described above is performed, but instead the elapsed time from sticking the pressure-sensitive adhesive sheet to the adherend becomes 24 hours. It was left in the standard environment described above. The laminated body was manufactured in the same manner as in Production Example 1 for other points. Table 1 shows the value of the adhesive strength after 12 hours at room temperature of each pressure-sensitive adhesive sheet as the adhesive strength during the partial removal step of Production Examples 3 and 4, and the adhesive strength after 24 hours of each pressure-sensitive adhesive sheet as the adhesive strength of the laminate. The value of is described.

(Production Example 5)
In Production Example 1, about 11 hours after the adhesive sheet D1 was attached to the adherend, the above heating (80 ° C., 5 minutes) was performed, and then the elapsed time after the adhesive sheet D1 was attached to the adherend. Was kept at room temperature until about 12 hours, followed by a partial removal step. The laminated body was manufactured similarly to the manufacture example 1 about the other point. In Table 1, the value of the adhesive strength after heating of the adhesive sheet D2 is described as the adhesive strength during the partial removal step of Production Example 5.

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

(Production Example 8)
A laminate was manufactured in the same procedure as in Production Example 1 except that the pressure-sensitive adhesive sheet D5 was used instead of the pressure-sensitive adhesive sheet D1. Table 1 shows the value of the adhesive strength after 12 hours at room temperature of the adhesive sheet D5 as the adhesive strength during the partial removal step of Production Example 8, and the value of the adhesive strength after heating of the adhesive sheet D5 as the adhesive strength of the laminate. is doing.

(Slit removability evaluation)
In the partial removal process of each production example, when the second region is peeled off from the adherend, if deformation such as elongation is not recognized on the adherend, “G” (pattern workability is good), When it was recognized, it was evaluated as “P” (poor pattern workability). The results are shown in Table 1.
In Production Examples 4 and 5, the second region could not be properly peeled off, so the following durability test was not performed. 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)
For the laminates obtained in Production Examples 1 to 3 and 6, 7 and 8, the planar body unloaded U-shaped expansion test machine “DLDM111LH” manufactured by Yuasa System Equipment Co., Ltd. and a jig (planar body unloaded U-shaped expansion / contraction) Using a test jig, a durability test was performed under the conditions of an expansion / contraction speed of 30 rpm, a bending radius of 3 mm, and the number of expansion / contraction times of 100 times.
Specifically, as shown in FIG. 6, after fixing both ends x and y of the sample 60 to the clamp portions 61 and 62 of the tester with a double-sided tape (not shown), the sample 60 is subjected to the above conditions. Was repeatedly expanded and contracted so that it was bent into a U shape with a bending radius of 3 mm with the adhesive sheet side inside from the flat state. When the sample 60 is bent, 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 sandwiched by the plate portions 63 and 64 separately installed from both sides with no load. I did it.
The state of the sample after 100 times expansion and contraction was visually observed. If no floating was observed between the adhesive sheet and the adherend, “G” (good durability), and “P” if floating was observed. (It is poor in durability). The results are shown in Table 1.

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

  Specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

Further, the matters disclosed by this specification include the following.
(1) A method for producing a laminate including an adherend and an adhesive piece partially covering the adherend, wherein the adhesive force of the adhesive piece to the adherend is 5 N / 25 mm or more,
An attaching step of attaching a pressure-sensitive adhesive sheet comprising a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface of the adherend side of the base material layer to the adherend;
A cutting step of cutting the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece in the adhesive sheet; and
A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;
In this order,
Here, the said partial removal process is a laminated body manufacturing method performed before the adhesive force with respect to the said adherend of the said adhesive sheet exceeds 2 N / 25mm.
(2) The method for producing a laminate according to (1) above, wherein the pressure-sensitive adhesive sheet is one having an adhesive strength of 2 N / 25 mm or less after 24 hours at 23 ° C. after being bonded to polyimide.
(3) The laminate manufacturing method according to (1) or (2), wherein heat treatment is performed after the partial removal step so that the adhesion of the first region to the adherend is 5 N / 25 mm or more. .
(4) The pressure-sensitive adhesive layer includes a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B that 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 production according to (1) or (2), wherein an ultraviolet irradiation treatment is performed after the partial removal step so that the adhesion of the first region to the adherend is 5 N / 25 mm or more. Method.
(6) The pressure-sensitive adhesive layer is composed of a photocurable composition containing a base polymer and a photocuring agent,
The photocuring agent is a polyfunctional (meth) acrylate,
Content of the said photocuring agent is a laminated body manufacturing method as described in said (5) which is 1 to 50 weight part with respect to 100 weight part of said base polymers.
(7) After the said partial removal process, it stores at normal temperature until the adhesive force with respect to the said adherend of the said 1st area | region becomes more than 5N / 25mm, The laminated body manufacture as described in said (1) or (2) 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 at least twice the thickness Ta of the pressure-sensitive adhesive layer. The laminated body manufacturing method in any one.
(9) The laminate manufacturing method according to any one of (1) to (8), wherein the second region is set so that at least one end of the second region reaches the end of the pressure-sensitive adhesive sheet.
(10) The laminate manufacturing method 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 pasting 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 pasting step, those including a plurality of units corresponding to the laminate,
The laminated body manufacturing method according to any one of (1) to (11), further including a dividing step of dividing the pressure-sensitive adhesive sheet and the adherend into the units as a step performed after the attaching step.
(13) An apparatus for carrying out the manufacturing method according to any one of (1) to (12),
An attaching mechanism for attaching the adhesive sheet;
A cutting mechanism for cutting the adhesive sheet;
A peeling mechanism for peeling the second region of the pressure-sensitive adhesive sheet;
The laminated body manufacturing apparatus containing this.

DESCRIPTION OF SYMBOLS 1 Laminated body 10 Adhered body 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 Laminate body manufacturing apparatus 51 Pasting mechanism 52 Cutting mechanism 53 Peeling mechanism 53

Claims (10)

A method for producing a laminate comprising an adherend and an adhesive piece partially covering the adherend, wherein the adhesive piece has an adhesive force of 5 N / 25 mm or more to the adherend,
An attaching step of attaching a pressure-sensitive adhesive sheet comprising a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface of the adherend side of the base material layer to the adherend;
A cutting step of cutting the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece of the adhesive sheet; and
A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;
In this order,
Here, the pressure-sensitive adhesive layer includes a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B that is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer,
The monomer component constituting the polymer A includes N-vinyl cyclic amide,
The amount of the N-vinyl cyclic amide used is 1% by weight or more and 40% by weight or less of the total amount of monomer components constituting the polymer A,
The partial removal step is performed before the adhesive strength of the adhesive sheet to the adherend exceeds 2 N / 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 adherend of said 1st area | region be 5 N / 25mm or more.   The method for producing a laminate according to claim 1, wherein the monomer component constituting the polymer A further contains a hydroxyl group-containing monomer. A method for producing a laminate comprising an adherend and an adhesive piece partially covering the adherend, wherein the adhesive piece has an adhesive force of 5 N / 25 mm or more to the adherend,
An attaching step of attaching a pressure-sensitive adhesive sheet comprising a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface of the adherend side of the base material layer to the adherend;
A cutting step of cutting the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece of the adhesive sheet; and
A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;
In this order,
Here, the pressure-sensitive adhesive layer includes a polymer A having a glass transition temperature of less than 0 ° C., and a polymer B that is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer,
The monomer component constituting the polymer A includes N-vinyl cyclic amide,
The amount of the N-vinyl cyclic amide used is 1% by weight or more and 40% by weight or less of the total amount of monomer components constituting the polymer A,
The partial removal step is performed before the adhesive strength of the adhesive sheet to the adherend exceeds 2 N / 25 mm,
The laminated body manufacturing method of storing at normal temperature until the adhesive force with respect to the said adherend of said 1st area | region becomes 5 N / 25mm or more after the said partial removal process.   The laminated body production according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive sheet is one having an adhesive strength of 2 N / 25 mm or less after 24 hours at 23 ° C after being bonded to polyimide. 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 any one of Claim 1 to 4 characterized by the above-mentioned. Laminate manufacturing method.   The laminate manufacturing method according to any one of claims 1 to 5, wherein the second region is set so that at least one end of the second region reaches an end of the pressure-sensitive adhesive sheet.   The laminate manufacturing method according to claim 6, 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. The laminate manufacturing method 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, those including a plurality of units corresponding to the laminate,
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 pasting mechanism for pasting the adhesive sheet;
A cutting mechanism for cutting the adhesive sheet;
A peeling mechanism for peeling the second region of the adhesive sheet;
The laminated body manufacturing apparatus containing this.

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