TW201934347A - Laminate production method - Google Patents

Abstract

Provided is a production method for a laminate that comprises an adherend and an adhesive piece that partially covers the adherend. The production method involves, in order: a gluing step for gluing onto the adherend an adhesive sheet, which comprises a base layer and an adhesive layer laminated on at least the adherend-side surface of the base layer; a cutting step for cutting the adhesive sheet at the boundary between a first region constituting the adhesive piece and a second region not constituting the adhesive piece; a partial removal step for peeling the second region off the adherend while leaving the first region on the adherend; and an adhesive strength-boosting step for boosting the adhesive strength of the first region to the adherend.

Description

Laminated body manufacturing method

The present invention relates to a method for manufacturing a laminated body.
This application claims priority based on Japanese patent applications 2017-253310 filed on December 28, 2017 and Japanese patent applications 2018-228924 filed on December 6, 2018. The content is incorporated into this specification as a reference.

By laminating one or two or more adhesive sheets to the adherend and using the above-mentioned adhesive sheet to locally cover the laminated body of the adherend, various patterns can be expressed corresponding to the shape or arrangement of the adhesive. As a method for manufacturing a laminated body that is partially covered by the adhesive body through the adhesive sheet as described above, for example, the following method is generally used: if the protective film of the circuit board is laminated, the adhesive sheet is cut into the required adhesive sheet in advance. The shape is such that the adhesive sheet and the adherend are aligned and attached. As a technical document related to such a technique, patent document 1 is mentioned.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2013-38379

[Problems to be solved by the invention]

However, in the above method, since the adhesive sheet is cut into a desired shape of the adhesive sheet in advance, and then the position alignment is performed to adhere to a specific adherend part, both cutting accuracy and attaching accuracy occur. error. Therefore, in the manufacture of miniaturized and high-definition electronic parts in the future, in order to manufacture products with good yields, there may be a need for very expensive equipment. In addition, for example, when the size of the cut adhesive sheet is large or the shape is complicated, it may become more difficult to adhere the adhesive sheet with good position accuracy and shape accuracy to the adherend.

Therefore, an object of the present invention is to provide a method for efficiently manufacturing a laminated body having a pattern of an adhesive sheet formed on an adherend with high accuracy. Related other inventions provide a device suitable for implementing the manufacturing method.
[Technical means to solve the problem]

With this specification, a method for manufacturing a laminated body including an adherend and an adhesive sheet partially covering the adherend is provided. The laminated body manufacturing method sequentially includes: an attaching step of attaching an adhesive sheet including a base material layer and an adhesive layer laminated on at least the surface of the adherend side of the base material layer to the adherend. A cutting step for cutting the boundary between the first region constituting the adhesive sheet and the second region not constituting the adhesive sheet in the adhesive sheet; a partial removing step for leaving the first region And peeling and removing the second region from the adherend on the adherend; and an adhesion increasing step, which increases the adhesion of the first region to the adherend.

According to the manufacturing method, by performing the attaching step, the cutting step, and the partial removal step in this order, a configuration in which the first region is arranged on the adherend with good shape accuracy and position accuracy can be obtained efficiently. In addition, since the adhesive force of the first region is increased after the second region is peeled from the adherend, the laminated body in which the first region is firmly bonded to the adherend can be manufactured, and it is easy to perform in the partial removal step. The operation of peeling the second region from the adherend.

In some aspects of the laminated body manufacturing method disclosed herein, the above-mentioned step of increasing the adhesive force may include heat treatment. This aspect can be implemented favorably using an adhesive sheet which shows the property that adhesive force rises greatly by heating. Examples of such an adhesive sheet include an adhesive sheet having an adhesive layer containing a polymer A having a glass transition temperature of less than 0 ° C. and a monomer having a polyorganosiloxane frame The polymer B, which is a copolymer with a (meth) acrylic monomer, is not limited thereto.

In several aspects, the monomer component constituting the polymer A described above may contain N-vinyl cyclic amidine. In the adhesive sheet using the polymer A containing the N-vinyl cyclic amidine as a constituent of the monomer as described above, the property that the adhesive force is greatly increased by heating can be exhibited well.

In other aspects of the method for manufacturing a laminated body disclosed herein, the above-mentioned step of increasing the adhesive force may include ultraviolet (UV) irradiation treatment. This aspect can be implemented favorably using an adhesive sheet which exhibits the property that adhesive force rises greatly by UV irradiation. An example of such an adhesive sheet is an adhesive sheet having an adhesive layer containing a photocurable composition containing a base polymer and a photohardener, and the photohardener is a polyfunctional (form Acrylate), and the content of the photocuring agent is 1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the base polymer, but is not limited thereto.

In any of the laminated body manufacturing methods disclosed herein, in the step of increasing the adhesive force, it is preferable to increase the adhesive force of the adhesive sheet to the adherend to more than twice that before the step. Thereby, the good peelability of the second region from the adherend in the partial removal step and the higher adhesion force of the adhesive sheet in the laminated body finally obtained to the adherend can be well achieved at the same time.

The partial removal step is preferably performed before the adhesive force of the adhesive sheet to the adherend exceeds 2 N / 25 mm. Thereby, damage or deformation of the adherend accompanying peeling of the second region can be more favorably suppressed.

The step of increasing the adhesive force may be, for example, a step of making the adhesive force of the adhesive sheet in the first region to the adherend to be 3 N / 25 mm or more. According to the manufacturing method including such an adhesive force raising step, a laminated body in which an adhesive sheet is firmly bonded to an adherend can be manufactured.

The second region is preferably set such that at least one end thereof reaches the end of the adhesive sheet. Thereby, the advantage of being easy to pick up the second region when performing the above-mentioned partial removal step can be obtained. From the viewpoint of improving the pick-up property, the second region may have a shape in which one end of the end of the adhesive sheet is widened toward the end of the adhesive sheet.

The manufacturing method disclosed herein can be implemented well in a manner that an adhesive sheet having an area of 2500 cm ² or more and a short side length of 50 cm or more is used for the above-mentioned attaching step. In the case of using the adhesive sheet having a large area and a wide width as described above, the advantages produced by adopting the manufacturing method disclosed herein can be more effectively utilized.

The manufacturing method disclosed herein may also be one in which the above-mentioned adhesive sheet and the adherend used in the above-mentioned attaching step include a plurality of units corresponding to the above-mentioned laminated body; The step further includes a dividing step of dividing the adhesive sheet and the adherend into the units. By thus sticking an adhesive sheet including a plurality of cells to an adherend and then dividing, a plurality of laminated bodies can be manufactured with high efficiency. In addition, the configuration of the plurality of units may be the same or different.

According to the present specification, a device for manufacturing a laminated body including an adherend and an adhesive sheet partially laminated on the adherend is provided. The device includes an attachment mechanism for attaching an adhesive sheet. The device may include a cutting mechanism for cutting the adhesive sheet. The device may include a peeling mechanism for peeling the second region. The device may include an adhesive force increasing mechanism for applying an adhesive force increase stimulus to the adhesive sheet. By using a manufacturing apparatus having such a configuration, any of the laminated body manufacturing methods disclosed herein can be well implemented.

Furthermore, a proper combination of the above-mentioned elements may also be included in the scope of the invention claimed by the patent application.

Hereinafter, preferred embodiments of the present invention will be described. With regard to matters other than the matters specifically mentioned in this specification and necessary for the implementation of the present invention, the operator can understand based on the instructions on the implementation of the invention and the technical common sense at the time of application. The present invention can be implemented based on the contents disclosed in this specification and technical common sense in the field.
Furthermore, in the drawings below, members and parts that perform the same function may be described with the same reference numerals, and repeated descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are modeled in order to clearly explain the present invention, and do not necessarily accurately indicate actual dimensions or scales.

＜＜ Manufacturing method of laminated body ＞＞
FIG. 1 is a flowchart showing a method for manufacturing a laminated body according to an embodiment, FIG. 2 is a perspective view of a laminated body manufactured by the method, and FIG. 3 is a sectional view taken along line III-III. As shown in FIGS. 2 and 3, the laminated body 1 manufactured by this embodiment includes an adherend 10 and adhesive sheets 21A and 21B that partially cover the surface 10A of the adherend 10. The adhesive sheets 21A and 21B are obtained by attaching the adhesive sheet 20 to the adherend 10 so that the first region 21 in the adhesive sheet 20 remains on the adherend 10 and the second region 22 is self-coated. The adherend 10 is peeled and removed, and is formed by the first region 21 remaining on the adherend 10. The adhesive sheet 20 has a structure in which a single area layer of the base material layer 202 has an adhesive layer 204.

As shown in FIG. 1, the laminated body manufacturing method of this embodiment includes an attaching step S10, a cutting step S20, a partial removing step S30, and an adhesive force increasing step S40 in this order.
In the attaching step S10, the adhesive sheet 20 is attached to the adherend 10. The adhesive sheet 20 used in this step includes: the first region 21 which is a region included in the constituent elements of the laminated body 1 as the adhesive sheets 21A and 21B, and the constituent elements which do not become the laminated body 1 and only in the laminated body 1 The second area 22 used in the manufacturing process. In the example shown in FIG. 2, a second region 22 extending linearly from one end in the longitudinal direction of the adhesive sheet 20 to the other end is set approximately at the center of the width of the adhesive sheet 20. In the adhesive sheet 20 used in the attaching step S10, the first region 21 and the second region 22 are physically connected, and these regions 21 and 22 can be treated as a continuous adhesive sheet 20.

In the cutting step S20, the boundary between the first region 21 and the second region 22 of the adhesive sheet 20 attached to the adherend 10 is cut. For example, as shown in FIG. 4, laser cutting is performed by irradiating laser light L along a planned cutting line C that constitutes a boundary between the first region 21 and the second region 22. In addition, FIG. 4 shows an example of laser cutting, but the method of cutting is not particularly limited, and it can be appropriately selected from various known cutting methods depending on the purpose or application. Examples of such a cutting method include a laser cutting using a laser light such as a CO ₂ laser or a YAG (Yttrium Aluminium Garnet) laser; a Thomson knife, a sharp knife, a rotary knife, Cutting of knives such as knives; cutting of blades, etc., but not limited to these. The cutting method may be used alone or in combination of two or more.

In the partial removal step S30, the first region 21 is left on the adherend 10, and the second region 22 is peeled off and removed from the adherend 10. For example, the second region 22 is peeled from one end in the longitudinal direction of the adhesive sheet 20 toward the other end. Thereby, as shown in FIGS. 2 and 3, the adhesive sheets 21A and 21B formed by the first region 21 are arranged on the adherend 10 spaced apart from each other, and the adhesive sheets are exposed and adhered between the adhesive sheets 21A and 21B. The structure of the body 10.

Then, in the adhesive force increasing step S40, the adhesive sheet 21A, 21B is given a stimulus that causes the adhesive force to increase. Thereby, the adhesive force of the adhesive sheets 21A and 21B to the adherend 10 is increased, and the laminated body 1 in which the adhesive sheets 21A and 21B are firmly adhered to the adherend 10 can be obtained. The content of the above stimulus can be appropriately selected according to the type of the adhesive sheet used and the like. Examples of the stimulus may include heating, irradiation with active light, press, and the like. These stimuli can be applied alone or in combination of two or more.

In the method for manufacturing a laminated body according to this embodiment, a portion of the adhesive sheet 20, that is, the second region 22 is peeled off from the adherend 10 after the adhesive sheet 20 is attached to the adherend 10, and A coating pattern including two adhesive sheets 21A and 21B arranged at a distance from each other is formed on the adherend 10. According to this method, the first region 21 constituting the two adhesive sheets 21A and 21B separated from each other in the laminated body 1 can be attached to the adherend 10 in the form of an adhesive sheet 20, and the adhesive sheet can be attached. At 20 o'clock, there is no need to adjust the relative positional relationship between the adhesive sheet 21A and the adhesive sheet 21B, thereby improving the manufacturing efficiency of the laminated body 1. In addition, since the boundary between the first region 21 and the second region 22 of the adhesive sheet 20 is cut after the adhesive sheet 20 is attached to the adherend 10, it is easy to improve the shape accuracy of the first region 21. Or relative to the position accuracy of the adherend 10. For example, in the attaching step S10, the adhesive sheet 20 is slightly shifted from the attachment position of the adherend 10, or the adhesive sheet 20 is slightly changed due to temperature changes or the release of internal stress. In the case of expansion and contraction, etc., it is also possible to eliminate or reduce these effects by adjusting the position or shape of the cutting process in the cutting step S20.

In the laminated body manufacturing method disclosed herein, after the second region 22 is peeled off and removed from the adherend 10, an adhesion increasing step S40 is performed to increase the adhesion of the adhesive sheets 21A and 21B to the adherend 10. Increasing the adhesive force of the adhesive sheets 21A and 21B is suppressed when the laminated body 1 is used, for example, a person's hand contacts the external force such as the adhesive sheet 21A, 21B, the deformation of the adherend 10, or the laminated body 1 is exposed to wind and rain or temperature changes From the viewpoint of environmental factors, it is preferable that the adhesive sheets 21A and 21B peel off or bulge from the adherend 10. On the other hand, in the partial removal step S30, if the adhesion of the second region 22 to the adherend 10 is too high, deformation such as elongation or surface peeling of the adherend 10 may occur when the second region 22 is peeled off. Or the second region 22 is broken in the middle of peeling and the like. According to the above manufacturing method, by performing the adhesive force raising step S40 after the second region 22 is peeled from the adherend 10, the laminated sheet 1 that is firmly bonded to the adherend 10 can be manufactured and partially removed. In step S20, the operation of peeling the second region 22 from the adherend 10 is easily performed.

The adhesive sheet contained in the laminated body manufactured by the method disclosed here is bonded to the adherend by an adhesive. Typically, the adhesive sheet includes a base material layer and an adhesive layer, and the adhesive sheet is bonded to the adherend via the adhesive layer. In this way, after the step of increasing the adhesive force, the adhesive sheet is also used to join the adherend with the adherend, that is, the adhesive maintains the required viscoelasticity. From the viewpoints of stress relaxation properties, low-temperature properties, and adhesion between the adherend and the adhesive sheet, it is preferable.

Furthermore, in the example shown in FIG. 2, the adhesive sheet 20 having the same size as the adherend 10 is attached so as to cover the entire surface (the entire area) of one side of the adherend 10, but the adhesive sheet The attachment state of the material to the adherend 10 is not limited to this. For example, the adhesive sheet may be attached in such a manner as to cover only a partial area on one side of the adherend, or may be attached in such a manner that a part of the adhesive sheet protrudes from the adherend. In addition, in the adhesive sheet used in the attaching step S10, the first region and the second region need only be connected to such an extent that the regions can be operated as a continuous sheet. Within this range, the first region and the second region can be connected. A cutting auxiliary structure such as a slit (perforation or the like) or a half cut is provided at the boundary between the area and the second area. Here, the half cut refers to a cut of a depth that does not penetrate the adhesive sheet in the thickness direction, and is typically formed as a cut of a depth that does not penetrate the base material layer in the thickness direction. Such a cut can be formed, for example, by making a processing blade from the back surface of the base material layer (the side opposite to the side of the laminated adhesive layer) to a depth that does not penetrate the base material layer. In one aspect, from the viewpoints of improving the operability of the adhesive sheet or reducing the manufacturing cost, the adhesive sheet having no cutting auxiliary structure provided at the boundary between the first region and the second region can be used well. In addition, a mark may be provided on the adhesive sheet used in the attaching step S10 to help align the position of the adhesive sheet with the adherend. The above marks may be structural marks such as through holes, cutouts, depressions, etc., may be visual marks formed by marks (such as printing or coloring) that can be optically inspected, or they may be based on the configuration of different components (for example, Identification of the attachment of labels, fixation of components capable of transmitting or reflecting signals). Such a mark may be provided at one or both of the first area and the second area, or may be provided at a boundary between the first area and the second area.

In the example shown in FIG. 4, in the cutting step S20, a continuous linear cutting process is performed at a depth penetrating the adhesive sheet to the surface of the adherend, but the cutting process is not limited to this. . For example, the first region and the second region after the cutting step S20 may be partially connected to each other by appropriately implementing the limit of the partial removal step S30. Examples of such cutting processing include discontinuous cutting processing such as perforation, half-cut processing, and processing that combines perforation and half-cut (for example, alternately repeating the slits that penetrate through the substrate layer and the substrate layer that does not penetrate) Depth of the cutting process). In addition, the cutting process may be performed through the depth of the adhesive sheet to the surface of the adherend, or may be performed through the adhesive sheet and further from the surface of the adherend to a certain depth, or may not be penetrated through the adhesive sheet. Depth (ie half cut). In the manufacturing method disclosed here, the adhesion is suppressed before the step compared to after the step of increasing the adhesive force, so it is preferable to perform the cutting process to completely separate the first region from the second region to At least to the depth of the substrate layer. This case may become advantageous from the viewpoints of improving the picking property of the second region in the partial removal step S30, preventing the bulge or offset of the first region, and improving the outer shape accuracy of the first region.

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. Setting the second area in such a manner that at least one end of the second area reaches the end of the adhesive sheet is preferable from the viewpoint of partially removing the picking property of the second area in step S30. In the state where the second region does not reach the end of the adhesive sheet, for example, the second region can be carried out by attaching a strong adhesive tape on the back of the second region at one end of the second region and pulling up. Of pickup. This picking method can also be used in a state where at least one end of the second region reaches the end of the adhesive sheet. In the laminated body manufacturing method disclosed herein, compared with after the adhesion increasing step, the adhesion before the adhesion increasing step is suppressed. As described above, the method of improving the second region by attaching the adhesive tape and pulling up is used. It is advantageous in terms of pickup.

In the aspect set in such a way that the second region reaches the end of the adhesive sheet, from the standpoint of pickup, the width of the second region reaching the end of the adhesive sheet is preferably set to 0.2 mm or more, but It is 0.5 mm or more, or 1 mm or more. In order to improve the picking property, the width of the second region may be increased when the second region reaches the vicinity of the end of the adhesive sheet. Further, from the viewpoint of miniaturization of a product (electronic device, etc.) including the laminated body obtained by the manufacturing method disclosed herein, the width of the second region reaching the end of the adhesive sheet is preferably set to 10 mm or less, more preferably 8 mm or less.

In the step of increasing the adhesive force, the degree of increasing the adhesive force is not particularly limited. Compared with the adhesive force before the step, the adhesive force after the step or the adhesive force of the laminated body obtained through the step becomes relatively high, that is, can. In several aspects, the step of increasing the adhesion force is preferably the adhesion force A ₀ [N / 25 mm] to the adherend before the step and the adhesion force A ₁ [N to the adherend after the step. / 25 mm] is performed in such a way that the ratio (A ₁ / A ₀ ) ≧ 2 is satisfied. That is, in the step of increasing the adhesive force, it is preferable to increase the adhesive force of the adhesive sheet to the adherend to be twice or more before the step. According to this step of increasing the adhesive force, there is a tendency that both the ease of removal of the second region in the partial removal step and the strong adhesion of the manufactured adhesive sheet of the laminated body to the adherend are achieved simultaneously. In several aspects, the ratio (A ₁ / A ₀ ) may be, for example, 3 or more, 5 or more, or 10 or more. The upper limit of the above ratio (A ₁ / A ₀ ) is not particularly limited, and from the viewpoint of suppressing the positional shift or bulge of the first region before the step of increasing the adhesive force, it is generally preferably 10,000 or less, 5000 or less, or 2000 or less . Each of the above-mentioned adhesive forces A ₀ and A ₁ can be measured in accordance with JIS Z0237 at 23 ° C. and 50% RH at a peeling angle of 180 degrees and a stretching speed of 300 mm / min. Grasp the peel strength of the adherend.

Furthermore, it is also considered that by using the selection of the adhesive sheet, after the partial removal step is attached to the adherend, the adhesion to the adherend is greatly increased by being left at room temperature for a long time. . However, in this aspect, it takes a long time for the adhesive sheet to be firmly bonded to the laminated body, and therefore it is not conducive to improving the productivity of the laminated body. According to the method for manufacturing a laminated body disclosed herein, a target laminated body can be obtained efficiently by performing an adhesive force increasing step for intentionally increasing the adhesive force after performing the partial removal step. From the viewpoint of the above productivity, the time for performing the adhesion increasing step is preferably 48 hours or less, more preferably 24 hours or less, even more preferably 12 hours or less, and even more preferably 6 hours or less. Good is less than 1 hour.

The second area to release the viewpoint of easiness, the adhesive sheet when the step of partially removing the adhesive force _P A is the body of the adhesive is preferably 2 N / 25 mm or less, but not particularly limited. That is, the partial removal step is preferably in the attaching step, before the adhesive force of the adhesive sheet attached to the adherend to the adherend exceeds 2 N / 25 mm (in other words, the adhesive force is suppressed after attaching). 2 N / 25 mm or less). In several aspects, the adhesion A _P may be less than 2 N / 25 mm, may be less than 1.5 N / 25 mm, may be less than 1.3 N / 25 mm, and may be less than 1 N / 25 mm. 0.8 N / 25 mm or less. The lower limit of the adhesive force A _P is not particularly limited. From the viewpoint of suppressing the position shift or bulging of the first region in the cutting step or the partial removal step, for example, it may be 0.005 N / 25 mm or more, and may be 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.

In addition, the adhesive force A ₀ of the adhesive sheet before the adhesive force increasing step to the adherend may be, for example, approximately the same as the adhesive force A _{P in} the local removal step. Therefore, each of the upper limit value and lower limit value of the adhesive force A _P exemplified above can also be independently applied to each of the upper limit value and the lower limit value of the adhesive force A ₀ . Further, each of the upper limit value and the lower limit of the above-exemplified adhesion of A _P may be applied independently to each of the following initial adhesion on B ₀ may be used by each of the limit value and the lower limit.

In the laminated body manufactured by the method disclosed herein, the adhesion force A _{F of the} adhesive sheet to the adherend may be, for example, 3 N / 25 mm or more, 5 N / 25 mm or more, and 7 N / 25 mm or more, 10 N / 25 mm or more, and 12 N / 25 mm or more are not particularly limited. From the viewpoint of suppressing the peeling or bulging of the adhesive sheet from the adherend when the laminated body is used, the adhesive force A _{F is} preferably high. The upper limit of the adhesive force A _F is not particularly limited. From the viewpoint of easily taking into account the ease of peeling of the second region in the partial removal step, the adhesive force A _F may be, for example, 50 N / 25 mm or less and 40 N / 25 mm or less in several aspects. , Can be 35 N / 25 mm or less, or 30 N / 25 mm or less.

Furthermore, the adhesive force A ₁ [N / 25 mm] of the adhesive sheet to the adherend after the step of increasing the adhesive force may be, for example, approximately the same as the adhesive force A _F of the laminated sheet to the adherend. Degree. Therefore, the upper limit values and lower limit values of the adhesive force A _F exemplified above can also be independently applied to each of the upper limit value and the lower limit value of the adhesive force A ₁ . In addition, each of the upper limit value and the lower limit value of the adhesive force A _F exemplified above may be independently applied to each of the upper limit value and the lower limit value of the adhesive force B ₁ after the stimulation described below.

The content of the stimulus imparted to the adhesive sheet in the step of increasing the adhesive force can be set, for example, as follows: the ratio of the initial adhesive force B ₀ of the used adhesive sheet to polyimide to the adhesive force B ₁ after the stimulation The adhesion rise ratio (B ₁ / B ₀ ) defined by the form satisfies a specific target value. The initial adhesive force B ₀ and the post-stimulation adhesive force B ₁ were measured by the methods described in the following examples.

In the manufacturing method disclosed herein, the step of increasing the adhesive force is preferably performed such that the ratio of increasing the adhesive force (B ₁ / B ₀ ) becomes, for example, 2 or more, and more preferably, the ratio of increasing the adhesive force (B ₁ / B ₀ ) Is performed in a manner of 3 or more, 5 or more, 10 or more, or 15 or more. In addition, from the viewpoint of reducing the load applied to the adhesive sheet and the adherend or improving the productivity of the laminated body, the adhesive force increasing step can increase the adhesive force increasing ratio (B ₁ / B ₀ ) to approximately 10,000 or less and 5,000 or less. Or the implementation below 2000. In several aspects, the adhesion increase ratio (B ₁ / B ₀ ) may be, for example, 1,000 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), and a device in which a display panel and a wiring board are integrated, a flexible substrate material is used in terms of heat resistance or dimensional stability. In many cases, a polyimide film is used as the substrate material. For polyimide, the adhesive sheet exhibiting the above-mentioned adhesive force B ₀ , B ₁ or the increase ratio of adhesive force (B ₁ / B ₀ ) is used in the manufacture of a laminated body with polyimide as an adherend. In the partial removal step, the peeling workability of the second region is good, and after the step of increasing the adhesive force or in the manufactured laminated body, the property of excellent adhesion with the adherend can be exhibited. By using this property, a film cover layer of FPC can be formed with high accuracy and efficiency. Therefore, the method disclosed herein can be favorably applied to, for example, the production of an FPC provided with a film cover layer.

The heating temperature in the case where heating is performed in the step of increasing the adhesive force as a stimulus to the adhesive sheet is not particularly limited, and workability, economy, and the base material layer or the adherend that can be included in the adhesive sheet can be considered. The heat resistance is set. The heating temperature may be, for example, less than 150 ° C, 120 ° C or lower, 100 ° C or lower, 80 ° C or lower, or 70 ° C or lower. The heating temperature may be, for example, 40 ° C. or higher, 50 ° C. or higher, or 60 ° C. or higher, 80 ° C. or higher, or 100 ° C. or higher. According to the 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. Alternatively, the adhesive sheet or the adherend may be heat-treated for a longer period of time (for example, 2 hours or longer, 5 hours or longer, etc.) to the extent that no significant thermal degradation occurs. The heat treatment may be performed once or may be performed in a plurality of times.

The adhesive sheet used in the attaching step may include only one region (the first region) in an adhesive sheet that becomes the adhesive sheet constituting the laminated body. For example, as shown in FIG. 2, it may include two first regions separated from each other. The region may also include three or more first regions. In the case where a piece of adhesive sheet includes a plurality of first regions, the shapes of the first regions may be the same or different. Similarly, the adhesive sheet used in the attaching step is contained in one adhesive sheet, for example, as shown in FIG. 4, it may include only a second region that is peeled off during the partial removal step, and may also include two or more or three More than. When a piece of adhesive sheet includes a plurality of second regions, the shapes of the second regions may be the same or different.

In several methods of manufacturing a laminated body, as the adhesive sheet and the adherend used in the attaching step, a plurality of units corresponding to the laminated body manufactured by the method can be used. This aspect may further include a step of dividing the adhesive sheet and the adherend into the units as a step performed after the attaching step. The above-mentioned dividing step may be performed at an arbitrary time after performing the attaching step. For example, the cutting step can be performed for a plurality of cells by performing the dividing step after at least the cutting step is ended. The manufacturing method disclosed herein can be performed at any stage such as (a) between the cutting step and the partial removal step, (b) between the partial removal step and the adhesion increasing step, and (c) after the adhesion increasing step. Implementation including the above-mentioned segmentation steps. One of the aspects (a) to (c) described above may be used or a combination of two or more may be used. Moreover, the said aspect (a) can be implemented favorably using the adhesive sheet provided with the following adhesive layer (2), for example. The said aspect (b) or said aspect (c) can be implemented favorably using the adhesive sheet provided with the following adhesive layer (1) or adhesive layer (2), for example.

＜＜ Manufacture Equipment ＞＞
The laminated body manufacturing method disclosed herein can be implemented, for example, using a laminated body manufacturing apparatus 50. As shown in FIG. 5, the laminated body manufacturing apparatus 50 includes an attachment mechanism 51 that attaches an adhesive sheet 20 to an adherend 10 A cutting mechanism 52 that cuts the boundary between the first region 21 and the second region 22 of the adhesive sheet 20; a peeling mechanism 53 that causes the first region 21 to remain on the adherend 10 and the second region 22 is peeled and removed from the adherend 10; and an adhesive force increasing mechanism 54 imparts a stimulus to the first region 21 to increase its adhesive force. Moreover, the manufacturing apparatus used for the laminated body manufacturing method which includes the aspect of a division process may further include the division mechanism which is not shown in figure.

The attaching mechanism 51 is constituted so as to be able to perform the attaching step in any of the manufacturing methods disclosed herein, and may include, for example, an adherend supply member, an adhesive sheet supply member, and a pressure-contact member of the adhesive sheet to the adherend. Wait for one or two or more. The cutting mechanism 52 is configured so that the cutting step in any of the manufacturing methods disclosed herein can be performed, and may include one or two or more cutting members as exemplified above. The peeling mechanism 53 is configured to perform a partial removal step in any of the methods disclosed herein, and may include, for example, one or two or more of a pickup member, a holding member, a peeling member, and the like in the second region. The adhesive force increasing mechanism 54 is configured to perform an adhesive force raising step in any of the methods disclosed herein by providing an stimulus to the adhesive sheet to increase the adhesive force of the adhesive sheet. The adhesive force raising mechanism 54 may include, for example, one or two or more of a UV irradiating member (a UV irradiating lamp, a mirror for adjusting an optical path, etc.), a heating member (a hot air heater, an infrared heater, an electric heater, etc.), and a pressure member. In addition, the division mechanism may be configured to use a known cutting method such as a Thomson knife, a sharp knife, a rotary knife, a knife, or the like, or a laser cutting method, a water jet cutting method, or a blade cutting method. The division method implements a division step.

＜＜ Adhesive sheet ＞＞
In the following, some examples of the adhesive sheet that can be suitably used to implement the laminated body manufacturing method disclosed herein are described, but it is not intended to limit the scope of the present invention.

The laminated body manufacturing method disclosed here can be favorably implemented using an adhesive sheet comprising a base material layer and an adhesive layer laminated on at least the adherend side of the base material layer. According to the adhesive sheet composed of the adhesive layer laminated on the base material layer, the adhesive layer can be reinforced by the aforementioned base material layer, so it is easy to peel off the second region from the adherend in the partial removal step.

＜ Base material layer ＞
As the base material layer, various film base materials can be favorably used. The film substrate may be a porous substrate such as a foam film or a nonwoven fabric sheet, may be a non-porous substrate, or may be a substrate having a structure in which a porous layer and a non-porous layer are laminated. In several aspects, as the above-mentioned film base material, those containing a resin film (self-supporting or non-dependent) capable of independently maintaining the shape can be favorably used as the base film. The "resin film" herein means a resin film having a non-porous structure and typically does not substantially contain air bubbles (no voids). Therefore, the concept of the resin film is different from a foam film or a nonwoven fabric. The resin film may have a single-layer structure or a multilayer structure with two or more layers (for example, a three-layer structure).

As the resin material constituting the resin film, for example, polyester, polyolefin, nylon 6, nylon 66, partially aromatic polyamide (PA), polyimide (PI), polyimide, etc. can be used. Imine (PAI), polyetheretherketone (PEEK), polyetherether (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate Ester copolymer (EVA), fluororesin such as polytetrafluoroethylene (PTFE), acrylic resin, polyacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride and other resins.

The resin film may be formed using a resin material containing one of these resins alone, or may be formed using a resin material containing two or more resin materials. 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, Resin films such as density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, and PP / PE blended film. Examples of resin films that are preferred from the viewpoint of strength or dimensional stability include PET films, PEN films, PPS films, and PEEK films. From the viewpoint of availability, PET films and PPS films are particularly preferred, and PET films are particularly preferred.

In the resin film, a light stabilizer, an antioxidant, an antistatic agent, a colorant (dye, pigment, etc.), a filler, a lubricating agent, and an anti-sticking agent can be blended within a range that does not significantly impede the effects of the present invention. A well-known additive such as a coupling agent.

The manufacturing method of a resin film is not specifically limited. For example, a conventionally known general resin film forming method such as extrusion molding, inflation molding, T-die cast molding, and calender roll molding can be suitably used.

The base material layer may be substantially composed of 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 adjustment layer (e.g., a coloring layer, an anti-reflection layer), a printing layer or a laminate layer for imparting a desired appearance to a base material layer, an antistatic layer, and an undercoat layer. , Peeling layer and other surface treatment layers.

Corrosion discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and primer coating using a primer can also be performed on the side of the adhesive layer in the base material layer. The formation of a layer is performed by a previously known surface treatment. This surface treatment may be a treatment for improving the grip of the adhesive layer to the substrate layer. The composition of the primer used for the formation of the primer layer is not particularly limited, and may be appropriately selected from known ones. The thickness of the undercoat layer is not particularly limited, but is generally preferably about 0.01 μm to 1 μm, and preferably about 0.1 μm to 1 μm. Examples of other processes to be performed on the substrate layer as needed include an antistatic layer forming process, a colored layer forming process, and a printing process. These processes can be applied individually or in combination.

＜＜ Adhesive layer ＞＞
The composition of the adhesive constituting the adhesive layer is not particularly limited. The adhesive may be an acrylic polymer, a rubber polymer, a polyester polymer, a urethane polymer, a polyether polymer, a polysiloxane polymer, or the like. Polyamide-based polymers and fluorine-based polymers are equivalent to one or two or more polymers that exhibit rubber elasticity at room temperature as the base polymer (the main component of the polymer component, that is, the component occupying more than 50% by weight) )By. Among them, acrylic adhesives and rubber-based adhesives can be exemplified as preferable adhesives. Here, the acrylic adhesive refers to an adhesive containing an acrylic polymer as a base polymer. The same applies to rubber-based adhesives. The above-mentioned acrylic polymer refers to a polymer in which 50% by weight or more of the total monomer components constituting the acrylic polymer are acrylic monomers. In addition, in the present specification, an acrylic single system refers to a monomer having at least one (meth) acrylfluorenyl group in one molecule. The above-mentioned (meth) acrylfluorenyl group includes the meanings of acrylfluorenyl and methacrylfluorenyl.

Some examples of adhesive layers that can be used well in the manufacturing methods disclosed herein include: (1) an adhesive layer containing a base polymer and a polymer containing a siloxane structure (hereinafter, also referred to as "adhesive Agent layer (1) ") and (2) an adhesive layer (hereinafter, also referred to as" adhesive layer (2) ") formed of a photocurable composition containing a base polymer and a photohardener. Hereinafter, the adhesive layer (1) and the adhesive layer (2) will be described in detail, but the adhesive sheet used in the manufacturing method disclosed herein is not limited to those having these adhesive layers.

<Adhesive layer containing base polymer A and siloxane-containing polymer B>
The adhesive layer (1) contains a base polymer A and a polymer B containing a siloxane structure, and exhibits the property that the adhesive force increases by heating. Therefore, it is possible to apply the heating in the adhesion improving step as a stimulus that causes an increase in adhesion to be favorably used in the method for manufacturing a laminated body disclosed herein. The adhesive layer (1) can be formed from an adhesive composition containing a base polymer A or a precursor thereof and a polymer B containing a siloxane structure. The form of the adhesive composition is not particularly limited, and may be, for example, various forms such as a water-dispersible type, a solvent type, a hot-melt type, and an active light-curable type (for example, a UV-curable type).

(Base polymer A)
As the base polymer A (hereinafter, sometimes simply referred to as "polymer A") of the adhesive layer (1), an acrylic polymer can be suitably used. When an acrylic polymer is used as the polymer A, there is a tendency that good compatibility with the polymer B is easily obtained. The good compatibility between polymer A and polymer B improves the mobility of polymer B in the adhesive layer, which can help to achieve both the low adhesion in the local removal step and the increase in adhesion (such as heating The strong adhesive layer (1) after the treatment) is preferred. Preferably, 50% by weight or more of the adhesive layer (1) is an acrylic polymer.

As the acrylic polymer, for example, those in which 40% by weight or more of the total monomer components constituting the acrylic polymer are alkyl (meth) acrylates can be suitably used. As the (meth) acrylic acid alkyl ester may be used in the ester having a carbon number 1 to the end of the well 20 (i.e., C _1-20 of) a straight-chain or branched-chain alkyl group of persons. In terms of easily achieving a balance of characteristics, the ratio of the C _1-20 alkyl (meth) acrylate in the total amount of constituent monomer components of the acrylic polymer may be, for example, 50% by weight or more, and may be 55% by weight. % Or more may be 60% by weight or more. For the same reason, the ratio of the C _1-20 alkyl (meth) acrylate in the total constituent monomer components may be, for example, 99.9% by weight or less, 98% by weight or less, or 95% by weight. the following. In several _aspects , the ratio of the (meth) acrylic acid C _1-20 alkyl ester in the total amount of the monomer components may be, for example, 90% by weight or less, 85% by weight or less, and 80% by weight or less. .

Specific non-limiting examples of the C _1-20 alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) ) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, pentyl (meth) acrylate Ester, isoamyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate 2 -Ethylhexyl, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, ( Undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, decyl (meth) acrylate Tetraalkyl ester, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, (meth) ) Isostearyl acrylate, (meth) acrylic Nonadecyl ester, (meth) acrylate, eicosyl acrylate.

Among these, at least C _1-18 alkyl (meth) acrylate is preferably used, and at least C _1-14 alkyl (meth) acrylate is more preferably used. In several aspects, the constituent monomer component of the acrylic polymer may include a C _4-12 alkyl (meth) acrylate (preferably a C _4-10 alkyl acrylate, such as a C _{6- 10} alkyl esters). 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 C _1-18 alkyl (meth) acrylates that can be used well include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), methyl 2-ethylhexyl acrylate (2EHMA), isostearyl acrylate (ISTA), and the like.

The constituent monomer component of the acrylic polymer may include an alkyl (meth) acrylate as a main component and, if necessary, other monomers (copolymerizable monomers) capable of copolymerizing with the alkyl (meth) acrylate. As a copolymerizable monomer, a monomer which has a polar group (for example, a carboxyl group, a hydroxyl group, etc.) can be used conveniently. The monomer having a polar group can help to introduce a cross-linking point to the acrylic polymer, or improve the cohesion of the acrylic polymer. The copolymerizable monomer may be used singly or in combination of two or more kinds.

Specific non-limiting examples of the copolymerizable monomer include the following.
Carboxyl-containing monomers: For example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, butenoic acid, methacrylic acid, and the like.
Hydroxyl-containing monomers: for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (meth) acrylic acid ( 4-hydroxymethylcyclohexyl) methyl esters and other hydroxyalkyl (meth) acrylates; N- (2-hydroxyethyl) acrylamidoamine (HEAA) and other monomers having a hydroxyl group and amidino group.
Nitrogen-containing monomers: for example, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiper, vinylpyridine, vinylpyrrole Imidazole, vinyloxazole, vinylline, N-vinyl-3-olinone, N-vinyl-2-caprolactam, N-vinyl-1,3-fluoren-2-one, N- Vinyl-3,5-line dione, N-acrylamidoline, N-vinylcarboxamide and the like.
In addition, cyano-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy-containing monomers, vinyl ether monomers, sulfo-containing monomers, phosphate-containing monomers, anhydride-containing monomers, etc. .

When such a copolymerizable monomer is used, the amount used is not particularly limited, and it is usually suitably set to 0.01% by weight or more based on the total amount of the monomer components. From the viewpoint of better exerting 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, and may also be 1% by weight or more. . The use amount of the copolymerizable monomer may be 50% by weight or less of the total amount of the monomer components, and preferably 40% by weight or less. Thereby, the cohesive force of the adhesive can be prevented from becoming too high, and the adhesion feeling at normal temperature (25 ° C) can be improved.

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

By using N-vinyl cyclic amidine, the cohesive force or polarity of the adhesive can be adjusted, and the adhesive force after heating (hereinafter, also referred to as "adhesive force after heating") as a stimulus for increasing the adhesive force can be improved. Specific examples of the N-vinyl cyclic amidine include those having a corresponding structure among the aforementioned nitrogen-containing monomers. Particularly preferred examples include N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam. The amount of N-vinyl cyclic ammonium amine used is not particularly limited, but it is generally suitable to be 0.01% by weight or more (preferably 0.1% by weight or more, such as 0.5% by weight or more) of the total amount of constituent monomer components of the acrylic polymer. ). In several aspects, the amount of N-vinyl cyclic amidine can be set to be more than 1% by weight of the total amount of the above monomer components, can be set to be 5% by weight or more, or 8% by weight or more. It may be 10% by weight or more, and may be 12% by weight or more. In addition, from the viewpoint of improving the stickiness at room temperature (25 ° C) or improving the flexibility at low temperature, the amount of N-vinyl cyclic ammonium amine used is generally suitably set to 40% by weight of the total amount of the monomer components. Hereinafter, it may be 30% by weight or less, 25% by weight or less, 20% by weight or less, or 18% by weight or less.

By using a hydroxyl-containing monomer, the cohesive force or polarity of the adhesive can be adjusted, and the adhesive force after heating can be improved. In addition, the hydroxyl-containing monomer provides a reaction point with the following crosslinking agent (for example, an isocyanate-based crosslinking agent), and the cohesive force of the adhesive can be improved by the crosslinking reaction. Preferred examples of the hydroxyl-containing monomer include 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4HBA), and N- (2-hydroxyethyl) acrylamide (HEAA). The use amount of the hydroxyl group-containing monomer is not particularly limited, and it is generally suitable to be 0.01% by weight or more (preferably 0.1% by weight or more, such as 0.5% by weight or more) of the total amount of constituent monomer components of the acrylic polymer. In several aspects, the use amount of the hydroxyl-containing monomer may be set to 1% by weight or more of the total amount of the monomer components, may be set to 5% by weight or more, and may also be set to 10% by weight or more. In addition, from the viewpoint of improving the stickiness at normal temperature (25 ° C) or improving the softness at low temperature, the amount of the hydroxyl-containing monomer used is generally suitably set to 40% by weight or less of the total amount of the above monomer components. It is 30% by weight or less, 20% by weight or less, and 10% by weight or 5% by weight or less.

In several aspects, as the copolymerizable monomer, N-vinyl cyclic amidine and a hydroxyl-containing monomer may be used in combination. In this case, the total amount of the N-vinyl cyclic amidine and the hydroxyl-containing monomer may be, for example, 0.1% by weight or more of the total monomer component of the acrylic polymer, may be 1% by weight or more, and may be 5% by weight or more, 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 amidine and the hydroxyl-containing monomer may be, for example, 50% by weight or less of the total amount of the monomer components, and preferably 40% by weight or less.

And treated with N- vinyl cyclic to Amides with aspects of the hydroxyl group-containing monomer, N- vinyl Amides of cyclic amount (W _N) relationship with the hydroxyl-containing monomer is used in an amount of (W _OH) ( Weight basis) is not particularly limited. 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, or 0.7 or more. The W _N / W _OH may be, for example, 100 or less, usually 20 or less, 10 or less, 5 or less, 2 or less, 1.5 or less, and 1.3 or less.

The Tg of polymer A is typically less than 0 ° C, preferably less than -10 ° C, and more preferably less than -20 ° C. The adhesive containing polymer A having a Tg of less than 0 ° C exhibits moderate fluidity (for example, the mobility of the polymer chain contained in the adhesive), and thus it is easy to perform a heat treatment in the adhesion increasing step. Increases the adhesive force significantly. In several aspects, the Tg of the polymer A may be, for example, less than -30 ° C, less than -40 ° C, less than -50 ° C, or less than -60 ° C. The lower limit of the Tg of the polymer A is not particularly limited. From the viewpoints of ease of material acquisition and improvement of cohesiveness of the adhesive layer, polymer A having a Tg of −80 ° C. or higher can generally be favorably used.

In the present specification, the Tg of a polymer refers to a nominal value described in a literature, a catalogue, or the like, or a Tg determined based on a Fox formula based on the composition of a monomer component used in the preparation of the polymer. The Fox formula is a relational formula between the Tg of the copolymer and the glass transition temperature Tgi of the 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 represents the glass transition temperature (unit: K) of the copolymer, Wi represents the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi represents the homopolymerization of monomer i. Glass transition temperature of the object (unit: K). In the case where the target polymer of the Tg is a homopolymer, the Tg of the homopolymer is the same as the Tg of the target polymer.

As the glass transition temperature of the homopolymer used to calculate Tg, a value described in known data is used. Specifically, the values in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) can be cited. For monomers having plural values described in the aforementioned Polymer Handbook, the highest value is adopted.

The weight average molecular weight (Mw) of the polymer A is generally suitably about 50,000 or more, but it is not particularly limited. From the viewpoint of obtaining an adhesive exhibiting better cohesiveness, it may be, for example, 100,000 or more, and may be 200,000 or more, 300,000 or more, 500,000 or more, or 700,000 or more. The Mw of the polymer A is generally preferably about 5 million or less. The polymer A of this Mw is easy to form an adhesive that exhibits moderate fluidity (movability of the polymer chain), and is therefore suitable for achieving an adhesive sheet having a high adhesion increase ratio. In several aspects, the Mw of the polymer A may be 3 million or less, may be 2 million or less, and may be 1.5 million or less.

In this specification, Mw of a polymer can be calculated | required by polystyrene conversion by gel permeation chromatography (GPC). More specifically, Mw can be measured according to the methods and conditions described in the following examples.

The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods of acrylic polymers, such as a solution polymerization method, an emulsion polymerization method, a block polymerization method, a suspension polymerization method, and a photopolymerization method, can be appropriately used. .

The initiator used for the polymerization may be appropriately selected from previously known thermal initiators, photoinitiators, and the like in accordance with the polymerization method. Non-limiting examples of thermal initiators include azo-based initiators such as 2,2'-azobisisobutyronitrile (AIBN), persulfates such as potassium persulfate, and peroxide-based Initiator, redox-based initiator, and the like. Non-limiting examples of the photoinitiator include benzoin ether-based photoinitiator, acetophenone-based photoinitiator, α-keto alcohol-based photoinitiator, and aromatic sulfonyl chloride-based photoinitiator. Initiator, photoactive oxime-based light initiator, benzoin-based light initiator, benzoin-based light initiator, benzophenone-based light initiator, ketal-based light initiator, 9-oxysulfur Photoinitiators, fluorenylphosphine oxide photoinitiators, and the like. The initiators may be used singly or in combination of two or more.

In several aspects, as a method for obtaining an acrylic polymer, a solution polymerization method can be favorably used. As a solvent for the solution polymerization, ethyl acetate, toluene, or the like can be used. The solution concentration is usually about 20 to 80% by weight. As the initiator, various known ones such as an azo system and a peroxide system 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 several aspects, the acrylic polymer can irradiate ultraviolet rays (UV) to the mixture obtained by formulating the initiator in the monomer component as described above to partially polymerize a part of the monomer component (acrylic Polymer slurry) in the form of an adhesive composition for forming an adhesive layer. The adhesive composition containing the acrylic polymer slurry can be applied to a specific object to be coated and irradiated with UV to complete the polymerization. That is, the above-mentioned acrylic polymer slurry can be understood as an acrylic polymer precursor. The adhesive layer (1) can be formed using the adhesive composition containing such an acrylic polymer slurry and polymer B, for example.

(Silicon structure-containing polymer B)
Polymer B containing a siloxane structure (hereinafter, sometimes referred to as "polymer B") is a monomer having a polyorganosiloxane structure (hereinafter, also referred to as "monomer S1") and (methyl) Copolymer of acrylic monomers. Polymer B has a low polarity and mobility derived from a polyorganosiloxane structure derived from monomer S1, and can function as an adhesion-increasing retarder that helps suppress the initial adhesion and increase the adhesion-increasing ratio. The monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane frame can be used. The monomer S1 promotes the polymer B to lean against the surface of the adhesive layer in the adhesive sheet before use (before attaching to the adherend) by the low polarity derived from its structure, and shows light peeling in the initial stage of bonding. Sex (low adhesion). As the monomer S1, a structure having a polymerizable reactive group at a single terminal can be suitably used. According to the copolymerization of such a monomer S1 and a (meth) acrylic monomer, a polymer B having a polyorganosiloxane skeleton in a side chain is formed. The polymer B of this structure is apt to become the one with lower initial adhesive force and higher adhesive force due to the mobility and ease of movement of the side chain.

As the monomer S1, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, examples of the single-end reactive silicone oil manufactured by Shin-Etsu Chemical Industry Co., Ltd. include X-22-174ASX, X-22-2426, X-22-2475, and KF-2012. The monomer S1 may be used singly or in combination of two or more kinds.
[Chemical 1]

[Chemical 2]

Here, R ³ in the general formulae (1) and (2) is hydrogen or a methyl group, 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 10,000 g / mol, and further preferably 850 g / mol or more and It is less than 6000 g / mol, particularly preferably more than 1500 g / mol and less than 5000 g / mol. If the functional group equivalent of the monomer S1 is less than 700 g / mol, the initial adhesion may not be sufficiently suppressed. When the functional group equivalent of the monomer S1 is 15000 g / mol or more, the increase in the adhesive force may become insufficient. If the functional group equivalent of the monomer S1 is within the above range, it is easy to adjust the compatibility (for example, the compatibility with the polymer A) or the mobility in the adhesive layer to a moderate range, and it is easy to achieve a high level of both. Adhesive sheet with low initial adhesion and strong adhesiveness when laminated body is used.

Here, the "functional group equivalent" means the weight of a main skeleton (for example, polydimethylsiloxane) bonded to each functional group. The labeling unit g / mol is converted to 1 mol of the functional group. The functional group equivalent of the monomer S1 can be calculated from, for example, the spectral intensity of ¹ H-NMR (proton NMR) based on nuclear magnetic resonance (NMR). Based on the functional group equivalent of the sum of spectral intensities monomer S1 ¹ H-NMR of (g / mol) can be calculated from the general structure of the analysis method of the related analytical spectroscopy based on ¹ H-NMR, as necessary of Japanese Patent Publication No. 5951153 describes the get on.

When two or more monomers having different functional group equivalents are used as the monomer S1, as the functional group equivalents of the monomer S1, an arithmetic average value can be used. That is, the functional group equivalent of the monomer S1 containing n kinds of monomers (monomer S1 ₁ , monomer S1 _2, ... monomer S1 _n ) having different functional group equivalents can be calculated by the following formula.
S1 functional group equivalent of the monomer (g / mol) = functionality (S1 _{monomer. 1} × monomers of group equivalent amount of formulation _{S1. 1} S1 ₂ + monomer having a functional group equivalent of the amount of formulation S1 × monomers of ₂ + ...... the monomer S1 + _n × functional group equivalent of the monomer blending amount of _n-S1) / (S1 _{formulation. 1} the formulation amount of the monomers of the monomer S1 + ₂ + ...... + the amount of the monomer formulation of _n-S1)

The content of the monomer S1 may be, for example, 5% by weight or more relative to all the monomer components used to prepare the polymer B. From the viewpoint of better exerting the effect as an adhesion-increasing retarder, it is preferably set to It may be 10% by weight or more, may be 15% by weight or more, and may be 20% by weight or more. From the viewpoint of polymerization reactivity or compatibility, the content of the monomer S1 is preferably 60% by weight or less, and may be 50% by weight or less with respect to all the monomer components used to prepare the polymer B. It may be 40% by weight or less, and may be 30% by weight or less. If the content of the monomer S1 is less than 5% by weight, the initial adhesion may not be sufficiently suppressed. When the content of the monomer S1 is more than 60% by weight, the increase in the adhesive force may become insufficient.

The monomer component used in the preparation of the polymer B contains, in addition to the monomer S1, a (meth) acrylic monomer capable of copolymerizing with the monomer S1. By copolymerizing one or two or more (meth) acrylic monomers with the monomer S1, the mobility of the polymer B in the adhesive layer can be well adjusted. Copolymerizing the monomer S1 with the (meth) acrylic monomer may also help improve the compatibility between polymer B and polymer A (for example, acrylic polymer).

Examples of the (meth) acrylic monomer include alkyl (meth) acrylate. For example, one or two or more of the monomers exemplified above for the alkyl (meth) acrylate which can be used when the polymer A is an acrylic polymer can be used as a copolymerization component of the polymer B. In several aspects, the polymer B may contain a C _4-12 alkyl (meth) acrylate (preferably a C _4-10 alkyl (meth) acrylate, such as a C _6- (meth) acrylate ₁₀ alkyl esters) as monomer units. In several other aspects, the polymer B may contain a C _1-18 alkyl methacrylate (preferably a C _1-14 alkyl methacrylate, such as a C _1-10 alkyl methacrylate) At least one of them is used as a monomer unit. The monomer unit constituting the polymer B may contain, for example, one or two or more kinds selected from MMA, BMA, and 2EHMA.

As another example of the said (meth) acrylic-type monomer, the (meth) acrylic acid ester which has an alicyclic hydrocarbon group is mentioned. For example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isoester (meth) acrylate, dicyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate can be used Wait. In several aspects, the polymer B may contain at least one selected from the group consisting of dicyclopentyl methacrylate, isomethacrylate, and cyclohexyl methacrylate as monomer units.

The amount of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid ester having an alicyclic hydrocarbon group may be, for example, 10% by weight or more and 95% by weight relative to the total monomer component used to prepare the polymer B. % Or less may be 20% by weight or more and 95% by weight or less, or 30% by weight or more and 90% by weight or less, 40% by weight or more and 90% by weight or less, or 50% by weight or more and 85% by weight or less.

As other examples of the monomer which can be contained together with the monomer S1 in the monomer units constituting the polymer B, various copolymers exemplified above can be cited as the monomers which can be used when the polymer A is an acrylic polymer. Sex monomer.

In some aspects, by making the monomer unit common to the monomer unit contained in the polymer B also contained in the polymer A, the mobility of the polymer B in the adhesive layer can be improved and the adhesion can be improved. Force rise ratio. The common monomer unit is effective when it is a component occupying 5 wt% or more of all the monomer units constituting the polymer B, and it is preferably 10 wt% or more (more preferably 20 wt% or more, such as 30 wt% or more). ingredient. The ratio of the above-mentioned common monomer units to all the 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 may also be 7% by weight. %the above. When the ratio of the common monomer unit to all the monomer units constituting the polymer A becomes high, the effect of improving the compatibility tends to be exhibited more favorably. In addition, considering the balance with other characteristics, the ratio of common monomer units to all monomer units constituting polymer A may be 50% by weight or less, 30% by weight or less, and 15% by weight. the following. Non-limiting examples of monomers that can be used as common monomer units include MMA, BMA, 2EHMA, methyl acrylate (MA), BA, 2EHA, cyclohexyl (meth) acrylate, (Meth) acrylate isoester, dicyclopentyl (meth) acrylate, and the like.

The Mw of the polymer B is not particularly limited. The Mw of the polymer B may be, for example, 1,000 or more, and may be 5,000 or more. From the viewpoint of improving the adhesiveness increase property caused by heating, in some aspects, the Mw of the polymer B may be, for example, 10,000 or more, 12,000 or more, 15,000 or more, or 17,000 or more. Can be more than 20,000. The Mw of the polymer B may be, for example, 500,000 or less, or may be 350,000 or less. In the partial removal step, from the viewpoint of easily peeling the second region from the adherend, in several aspects, the Mw of the polymer B may be, for example, 100,000 or less, 70,000 or less, or 50,000 or less, It can be less than 50,000, it can be less than 40,000, it can be less than 35,000, it can be less than 30,000, it can be less than 28,000, or it can be less than 25,000. If the Mw of the polymer B is within the range of any of the above upper and lower limits, it is easy to adjust the compatibility or mobility in the adhesive layer to a moderate range, and it is easy to achieve local removal at a higher level at the same time. Low adhesion in the step and strong adhesion after the step of increasing the adhesion.

The polymer B can be produced, for example, by polymerizing the monomers by a known method such as a solution polymerization method, an emulsion polymerization method, a block polymerization method, a suspension polymerization method, and a photopolymerization method.

In order to adjust the molecular weight of the polymer B, a chain transfer agent can be used. Examples of the chain transfer agent used include octyl mercaptan, lauryl mercaptan, third nonyl mercaptan, third (dodecyl) mercaptan, mercaptoethanol, and α-thioglycerol. Thiol compounds; Thioglycolic acid; Methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, third butyl thioglycolate, thioglycolic acid 2-ethylhexyl ester, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, thioglycolate of ethylene glycol, neopentyl Thioglycolates such as thioglycolates of diols and thioglycolates of pentaerythritol; α-methylstyrene dimers, etc.

The use amount of the chain transfer agent is not particularly limited, but it is generally suitably set to 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.2 to 100 parts by weight of the monomer. Parts to 10 parts by weight. By adjusting the use amount of the chain transfer agent in this way, a polymer B having a preferable molecular weight can be obtained. The chain transfer agent may be used singly or in combination of two or more kinds.

The used amount of the polymer B is 100 parts by weight relative to the used amount of the polymer A. For example, it can be set to 0.1 parts by weight or more. From the viewpoint of obtaining a higher effect, it can be set to 0.3 parts by weight or more, and can be set to 0.4. Although it is 0.5 weight part or more, it may be 1 weight part or more, or 2 weight part or more, but it does not specifically limit. From the viewpoint of avoiding excessive reduction in cohesion, the amount of polymer B used may be, for example, 75 parts by weight or less, 50 parts by weight or less, and 20 parts by weight or less with respect to 100 parts by weight of polymer A. It may be 10 parts by weight or less, 8 parts by weight or less, and 5 parts by weight or less.

The adhesive layer may contain a polymer (an arbitrary polymer) other than the polymer A and the polymer B as needed, as long as the effect obtained by the technology disclosed herein is not significantly impaired. The use amount of such an arbitrary polymer is usually suitably set to 20% by weight or less of the total polymer components contained in the adhesive layer. In several aspects, the amount of the above-mentioned arbitrary polymer may be 5% by weight or less, and may also be 1% by weight or less. It may also be an adhesive layer which does not substantially contain polymers other than polymer A and polymer B.

(Crosslinking agent)
In the adhesive layer, a cross-linking agent can be used as necessary for the purpose of adjusting cohesion and the like. As the cross-linking agent, cross-linking agents known in the field of adhesives can be used, and examples thereof include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, Carbodiimide-based crosslinking agents, metal chelate-based crosslinking agents, and the like. Particularly preferred are isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents. The crosslinking agents may be used singly or in combination of two or more kinds. The technique disclosed here can be implemented well using at least an isocyanate-based crosslinking agent as the crosslinking agent.

Examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone di Cycloaliphatic isocyanates such as isocyanates; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane / toluene diisocyanate three Polymer adducts (e.g. "Coronate L" manufactured by Tosoh), trimethylolpropane / hexamethylene diisocyanate terpolymer adducts (e.g. "Coronate HL" manufactured by Tosoh), xylylenediamine Isocyanate trimethylolpropane adducts (such as "Takenate D110N" manufactured by Mitsui Chemicals, isocyanurate bodies of hexamethylene diisocyanate (such as "Coronate HX" manufactured by Tosoh), etc. .

Examples of the epoxy-based crosslinking agent include bisphenol A, an epichlorohydrin-type epoxy resin, ethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl. Ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N, N, N ', N'-tetraglycidyl group Xylylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane.

When the crosslinking agent is used, the amount used is not particularly limited, and for example, it can be set to an amount exceeding 0 parts by weight based on 100 parts by weight of the polymer A. In several aspects, the amount of the cross-linking agent used may be, for example, 0.01 parts by weight or more, 0.05 parts by weight or more, or 0.1 parts by weight, 0.5 parts by weight or more, relative to 100 parts by weight of the polymer A. 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more. By increasing the amount of cross-linking agent used, there is a tendency to obtain higher cohesion. On the other hand, from the viewpoint of avoiding a decrease in viscosity due to an excessive increase in cohesive force, the amount of the crosslinking agent to be used is usually 15 parts by weight or less relative to 100 parts by weight of the polymer A, and may be set to 10 It may be 5 parts by weight or less. The use amount of the cross-linking agent is not too much. It may also be advantageous from the viewpoint of utilizing the fluidity of the adhesive to better exhibit the use effect of the polymer B.

In order to perform the crosslinking reaction more efficiently, a crosslinking catalyst may be used. Examples of the cross-linking catalyst include metal-based cross-linking catalysts such as tetra-n-butyl titanate, tetra-isopropyl titanate, iron acetoacetone, butyl tin oxide, and dioctyl tin dilaurate. Among them, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferred. The use amount of the cross-linking catalyst is not particularly limited. For example, it can be set to about 0.0001 to 1 part by weight (typically 0.05 part by weight or less) based on 100 parts by weight of the polymer A.

If necessary, a polyfunctional monomer may be used in the adhesive layer. The polyfunctional monomer can be used for the purpose of adjusting the cohesive force, etc. by replacing or using the cross-linking agent in combination with the cross-linking agent. For example, a polyfunctional monomer can be used favorably in the adhesive layer formed from a photocurable adhesive composition.
Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 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 (methyl) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra Methylol methane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, acrylic urethane, Butanediol (meth) acrylate, hexanediol di (meth) acrylate, and the like. Among them, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be favorably used. The polyfunctional monomer may be used singly or in combination of two or more kinds.

The used amount of the polyfunctional monomer varies depending on the molecular weight, the number of functional groups, and the like, and is generally suitably set to a range of about 0.01 to 3.0 parts by weight based on 100 parts by weight of the polymer A. In several aspects, the amount of the polyfunctional monomer used may be, for example, 0.02 parts by weight or more and 0.03 parts by weight or more relative to 100 parts by weight of the polymer A. By increasing the amount of the polyfunctional monomer used, a higher cohesive force tends to be obtained. On the other hand, from the viewpoint of avoiding a decrease in viscosity due to an excessive increase in cohesive force, the amount of the polyfunctional monomer used may be 2.0 parts by weight or less and may be 1.0 weight based on 100 parts by weight of polymer A It may be 0.5 parts by weight or less. The use amount of the polyfunctional monomer is not too much, which may be advantageous from the viewpoint of utilizing the fluidity of the adhesive to better express the use effect of the polymer B.

(Adhesion imparting resin)
The adhesive layer may contain an adhesion-imparting resin as needed. The adhesion-imparting resin is not particularly limited, and examples thereof include rosin-based adhesion-imparting resin, terpene-based adhesion-imparting resin, phenol-based adhesion-imparting resin, hydrocarbon-based adhesion-imparting resin, ketone-adhesion-impart resin, and polyamide adhesion Resin imparting, epoxy-based adhesive imparting resin, elastic system adhesive imparting resin, and the like. The adhesion-imparting resin may be used alone or in combination of two or more.

In a state in which the adhesive layer contains the adhesion-imparting resin, the content of the adhesion-imparting resin is not particularly limited, and it can be set in such a manner as to exert appropriate adhesion performance depending on the purpose or application. The content of the adhesion-imparting resin with respect to 100 parts by weight of the polymer A (the total amount when the two or more adhesion-imparting resins are contained) can be set to about 5 to 500 parts by weight, for example. In addition, the technology disclosed herein can also adhere to a resin content of less than 5 parts by weight, less than 2 parts by weight, or less than 1 part by weight relative to 100 parts by weight of polymer A, or the adhesive layer can be substantially The implementation without the adhesion-imparting resin is well performed.

As the adhesion-imparting resin, those having a softening point (softening temperature) of about 80 ° C. or higher (preferably about 100 ° C. or higher, for example, about 120 ° C. or higher) can be favorably used. The adhesion-imparting resin having a softening point of the above lower limit value or more tends to effectively improve the initial low adhesion and the strong adhesion when the laminate is used. The upper limit of the softening point is not particularly limited, and may be, for example, about 200 ° C or lower (typically 180 ° C or lower). The softening point of the adhesion-imparting resin can be measured based on the softening point test method (ring and ball method) specified in JIS K2207.

(Formation of adhesive layer)
The adhesive layer (1) may be a hardened layer of the adhesive composition. That is, the adhesive layer (1) can be formed by applying an adhesive composition such as a water-dispersible type, a solvent type, a photo-hardening type, a hot-melt type, or the like to an appropriate surface and then performing a curing treatment as appropriate. When two or more types of hardening treatments (drying, crosslinking, polymerization, cooling, etc.) are performed, these can be performed simultaneously or in multiple stages. In the adhesive composition of a part of the polymer (acrylic polymer slurry) using a monomer component, the final copolymerization reaction is typically performed as the above-mentioned hardening treatment. That is, a part of the 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 performed. Hardening treatments such as cross-linking and drying can also be performed if necessary. For example, when it is necessary to dry with a photocurable adhesive composition, it is sufficient to perform photocuring after drying. In the adhesive composition using a complete polymer, typically, as the above-mentioned hardening treatment, treatments such as drying (heat-drying) and crosslinking are performed as necessary.

For the application of the adhesive composition, for example, a gravure roll coater, a reverse roll coater, a touch roll coater, a dip roll coater, a bar coater, a blade coater, a spray coater, or the like can be used. The conventional coating machine is used. The coating of the adhesive composition used for the formation of the following adhesive layer (2) and other adhesive compositions can also be performed in the same manner.

<Adhesive layer formed from a photocurable composition containing a base polymer P and a photohardener>
The adhesive layer (2) contains a base polymer P and a photo-hardening agent, and exhibits a property of being hardened by irradiation with active light (for example, UV) to improve adhesion. Therefore, the irradiation of active light in the adhesion improvement step can be favorably used in the laminated body manufacturing method disclosed herein as a stimulus that causes an increase in adhesion. From the viewpoint of improving the curing efficiency by irradiation with active light, the adhesive composition (photocurable composition) constituting the adhesive layer (2) preferably contains a photoinitiator. From the viewpoint of suppressing the phenomenon that the adhesive layer is hardened before photo-hardening and the adhesive sheet remains on the adherend when the adhesive sheet in the second region is peeled and removed in the partial removal step, that is, the paste remaining phenomenon Preferably, a crosslinked structure is introduced into the base polymer P.

(Base polymer P)
As the base polymer P (hereinafter, sometimes referred to simply as "polymer P") of the adhesive layer (2), an acrylic polymer can be suitably used from the viewpoint of optical transparency and the like. For example, 50% by weight or more of the adhesive layer (2) is preferably an acrylic polymer. As the acrylic polymer, an alkyl (meth) acrylate in which 40% by weight or more of the total constituent monomer components are the same as the polymer A described above can be used favorably.

The acrylic polymer preferably contains a monomer component having a functional group capable of crosslinking as a copolymerization component. Examples of the monomer having a functional group capable of crosslinking include a hydroxyl-containing monomer or a carboxyl-containing monomer. Examples of the hydroxyl-containing monomer and the carboxyl-containing monomer include the same monomers as those exemplified as the constituent monomer component of the polymer A contained in the adhesive layer (1). Among these, it is preferable to contain a hydroxyl-containing monomer. The hydroxyl group or carboxyl group of the polymer P becomes a reaction point with the following crosslinking agent. By introducing a cross-linked structure to the polymer P, the cohesive force is improved, the adhesiveness of the adhesive layer (2) is improved, and the fluidity of the adhesive is reduced. Therefore, there is a tendency that the paste residue in the adherend is reduced during the partial removal step. .

In the acrylic polymer, the total amount of the hydroxyl-containing monomer and the carboxyl-containing monomer is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and still more preferably 5 to 3% by weight based on the total amount of the constituent monomer components. 20% by weight. It is particularly preferred that the content of the (meth) acrylate containing a hydroxyl group is in the above range.

The acrylic polymer preferably contains a nitrogen-containing monomer as a constituent monomer component. Examples of the nitrogen-containing monomer include the same monomers as those exemplified as the constituent monomer component of the polymer A contained in the adhesive layer (1). The content of the nitrogen-containing monomer is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and still more preferably 5 to 20% by weight based on the total amount of the constituent monomer components. The acrylic polymer preferably contains N-vinylpyrrolidone as a nitrogen-containing monomer within the above range.

When the acrylic polymer contains both a hydroxyl-containing monomer and a nitrogen-containing monomer as monomer components, there is a tendency that the cohesive force and transparency of the adhesive are improved. In the acrylic polymer, the total amount of the hydroxyl-containing monomer and the nitrogen-containing monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 15 to 50% by weight based on the total amount of the constituent monomer components. 35% by weight.

The acrylic polymer may contain monomer components other than the above, such as cyano-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy-containing monomers, vinyl ether monomers, and sulfo-containing monomers. , Phosphate group-containing monomers, acid anhydride group-containing monomers, and the like.

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

The acrylic polymer can be obtained by various known polymerization methods in the same manner as the polymer A contained in the adhesive layer (1). For example, a solution polymerization method can be favorably used.

The adhesion of the adhesive layer before photo-curing is easily affected by the constituent components and molecular weight of the polymer P. From the viewpoint of achieving both moderate adhesion and suppression of paste residue in the local removal step, the weight average molecular weight of the acrylic polymer is preferably 100,000 to 5 million, more preferably 300,000 to 3 million, and even more preferably It is 500,000 to 2 million. When a crosslinked structure is introduced into the polymer P, the molecular weight of the polymer P refers to the molecular weight before the crosslinked structure is introduced.

(Crosslinking agent)
From the viewpoint of imparting an appropriate cohesive force to the adhesive, it is preferable to introduce a crosslinked structure into the polymer P. For example, a cross-linking structure is introduced by adding a cross-linking agent to the solution after polymerizing the polymer P and heating it as necessary. Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, a carbodiimide-based crosslinking agent, and a metal chelate. Cross-linking agents. These crosslinking agents react with a functional group such as a hydroxyl group introduced into the polymer P to form a crosslinked structure. As the isocyanate-based crosslinking agent, the same one as the adhesive layer (1) can be used.

The amount of the crosslinking agent used may be appropriately adjusted according to the composition, molecular weight, and the like of the polymer P. The amount of the cross-linking agent to be used is, 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, and even more preferably 1 to 4 parts with respect to 100 parts by weight of the polymer P. Parts by weight. In order to promote the formation of a cross-linked structure, a cross-linking catalyst may be used in the same manner as the adhesive layer (1).

(Light hardener)
The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer (2) is configured to exhibit a light-curing property by containing a light-curing agent in addition to the polymer P. The adhesive layer (2) exhibits the following properties: by irradiating active light after bonding with the adherend, as a stimulus for increasing the adhesive force, light curing is performed to improve the adhesive force.

As the photocuring agent, a photocurable monomer or a photocurable oligomer can be used. As the photohardening agent, a compound having two or more ethylenically unsaturated bonds in one molecule is preferred. The photo-curing agent is preferably a compound exhibiting compatibility with the polymer P. In terms of exhibiting a moderate compatibility with the polymer P, the photohardener is preferably a liquid at normal temperature. The photohardening agent is compatible with the polymer P and is uniformly dispersed in the composition, thereby ensuring a contact area with the adherend and forming an adhesive layer (2) having high transparency.

The compatibility of the polymer P with the light hardener is mainly affected by the structure of the compound. The structure and compatibility of a compound can be evaluated by, for example, Hansen solubility parameters. The smaller the difference between the solubility parameters of the polymer P and the photohardener, the higher the compatibility tends to become.

In terms of high compatibility with an acrylic polymer, it is preferable to use a polyfunctional (meth) acrylate as a light hardener. Examples of the polyfunctional (meth) acrylate 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 isotricyanate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, (meth) acrylate urethane, epoxy (formaldehyde) Group) acrylate, butadiene (meth) acrylate, isoprene (meth) acrylate, and the like.

The compatibility of the polymer P with the light hardener is also affected by the molecular weight of the compound. The smaller the molecular weight of the photocurable compound, the higher the compatibility with the polymer P tends to be. From the viewpoint of compatibility with the polymer P, the molecular weight of the photocuring agent is preferably 1500 or less, and more preferably 1,000 or less.

The type or content of light hardener mainly affects the adhesion after light hardening. The smaller the functional group equivalent (that is, the larger the number of functional groups per unit molecular weight), the larger the content of the photohardening agent, and the larger the adhesive force after photohardening tends to become.

From the viewpoint of improving the adhesion after light curing, the functional group equivalent (g / eq) of the light curing agent is preferably 500 or less, and more preferably 450 or less. On the other hand, if the photocrosslinking density is excessively increased, the viscosity of the adhesive may be reduced, which may result in a decrease in adhesion. Therefore, the functional group equivalent of the photocuring agent is preferably 100 or more, more preferably 130 or more, even more preferably 150 or more, and even more preferably 180 or more.

In the combination of an acrylic polymer and a polyfunctional acrylate light hardener, when the functional group equivalent of the light hardener is small, the interaction between the polymer P and the light hardener is strong, and there is adhesion before light hardening. Tendency to become higher. In the technique disclosed herein, from the viewpoint of suppressing the adhesive force before photocuring to an appropriate range and improving the removability of the second region in the partial removal step, the functional group equivalent of the photocuring agent is also preferred. Within the above range.

The content of the light hardener in the adhesive composition is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and still more preferably 10 to 35 parts by weight based on 100 parts by weight of the polymer P. When the photocurable compound is contained in the adhesive composition as an uncured (unreacted) monomer or oligomer, a photocurable adhesive layer can be obtained. In order to make the light hardener contained in the composition in an uncured state, it is preferable to add the light hardener to the polymer solution after polymerizing the polymer P.

If the content of the light hardening agent in the adhesive composition becomes large, the light hardening agent easily leaks out to the surface of the adhesive layer. If the light hardening agent oozes out in large amounts, it is easy to leave the light hardening agent on the adherend after removing the second region. On the other hand, by exuding a small amount of light curing agent to the surface, the adhesion of the adhesive layer to the adherend can be suppressed, and the low adhesion before light curing and the strong adhesion after light curing can be achieved simultaneously.

(Light initiator)
The adhesive layer (2) preferably contains a photoinitiator. The photoinitiator generates active species through the irradiation of active light to promote the curing reaction of the photohardener. As a photoinitiator, a photocationic initiator (photoacid generator), a photoradical initiator, a photocationic initiator (photobase generator), etc. can be used according to the kind of photohardening agent and the like. In the case where a polyfunctional acrylate is used as the light hardener, it is preferable to use a photoradical initiator. Examples of the photo-radical initiator include hydroxy ketones, benzophenone dimethyl ketals, amino ketones, fluorenyl phosphine oxides, benzophenones, and tri-derivatives containing trichloromethyl Things. The photo radical generator may be used alone or in combination of two or more. The content of the light initiator in the adhesive layer is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the adhesive layer.

(Other additives)
In addition to the components exemplified above, the adhesive layer may also contain a silane coupling agent, an adhesiveness imparting agent, a plasticizer, and a softening agent within a range that does not greatly impair the effect obtained by the technology disclosed herein. , Anti-deterioration agents, fillers, colorants, ultraviolet absorbers, antioxidants, surfactants, antistatic agents and other additives.

(Formation of adhesive layer)
The adhesive layer (2) can be formed, for example, by applying an adhesive composition containing a polymer P, a light hardener, and other components used as needed, to an appropriate surface, and drying and removing the solvent as necessary. As a drying method, an appropriate method can be used suitably. The heating and drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and even more 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 adhesive composition contains a cross-linking agent, it is preferred to perform the cross-linking by heating or aging while drying the solvent or after drying the solvent. The heating temperature or heating time is appropriately set according to the type of the cross-linking agent to be used, and is usually cross-linked by heating in the range of 20 ° C to 160 ° C for about 1 minute to 7 days. The heating used for drying and removing the solvent can also be used for the heating of crosslinking. After the cross-linking agent is used to introduce a cross-linked structure to the polymer, the photohardener also maintains an unreacted state. Therefore, a photocurable adhesive layer (2) containing the polymer P into which the crosslinked structure is introduced and an unreacted photocuring agent is formed.

(Friction)
Regarding the adhesive layer (2) before photo-hardening, from the viewpoint of easily suppressing the adhesive force, it is preferable that the frictional force at a frequency of 5 Hz measured by a tapping mode of a friction force microscope (FFM) is a frequency of 0.1 2 to 5 times the friction at Hz. In addition, when the ratio of the frictional force between the frequency of 0.1 Hz and 5 Hz of the adhesive layer (2) is in this range, the adhesive force after photo-hardening tends to increase significantly compared with that before photo-hardening.

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

The frictional force obtained by nano-tribology reflects the tendency of the adhesion between the surface of the adhesive layer and the adherend. A small frictional force means that the surface of the adhesive is close to a liquid and has a low viscosity. When the surface of the adhesive layer is tacky, the frictional force becomes large, and the frictional force measured by the FFM exhibits frequency dependence. The frictional force measured at a specific frequency easily reflects the physical properties of each of the constituent components of the adhesive composition. On the other hand, the frequency dependency tends to more accurately reflect the characteristics of the surface. The smaller the frequency dependence of the friction force, the smaller the viscosity, the stronger the liquid properties, and the greater the frequency dependence of the friction force, the greater the viscosity, and the higher the adhesion to the adherend. For example, when the base polymer of the adhesive layer and the light hardener are not completely compatible, the liquid light hardener oozes out to the surface, and a bonding layer (WBL, Weak Boundary) is formed at the bonding interface with the adherend. Layer), the characteristics of the liquid state are stronger, so there is a tendency that the friction force and the frequency dependence of the friction force become smaller.

By controlling the compatibility between the polymer P in the adhesive layer (2) and the light hardener, a small amount of light hardener leaks out to the surface of the adhesive layer to form WBL. If the WBL is formed moderately, the characteristics of the surface (and then the interface) change, and the frequency dependence of the frictional force and frictional force becomes small. Thereby, peeling of the second region in the partial removal step is easily performed.

When the friction force at a frequency of 5 Hz of the adhesive layer before light hardening is 5 times or less than the friction force at a frequency of 0.1 Hz, peeling of the adhesive layer and the adherend before light hardening becomes easy. tendency. From the viewpoint of preventing the light hardener from oozing out, the friction force of the adhesive layer at a frequency of 5 Hz is preferably more than twice the friction force at a frequency of 0.1 Hz, more preferably 3 times or more, and even more preferably 3.5. Times more.

From the viewpoint of simultaneously achieving moderate adherence and peelability to the adherend, the FFM differential signal at 5 Hz of the adhesive layer before photo-hardening measured using a cantilever with a spring constant of 40 N / m is better It is 0.01 to 1 V, more preferably 0.05 to 0.9 V, still more preferably 0.1 to 0.8 V, and even more preferably 0.2 to 0.7 V.

From the viewpoint of improving the adhesion after photo-hardening, it is preferable that the friction force at a frequency of 5 Hz measured by the FFM after the photo-hardening of the adhesive layer is more than 5 times the friction force at a frequency of 0.1 Hz. More preferably, it is 5.5 times or more. The FFM differential signal of the light-hardened adhesive layer measured at 5 Hz using a cantilever with a spring constant of 40 N / m is preferably 0.1 V or more, more preferably 0.2 V or more, and even more preferably 0.3 V or more. From the viewpoint of improving the adhesive force, the larger the frictional force of the adhesive layer after photo-hardening, the better. Therefore, the upper limit of the friction force is not particularly limited. The FFM differential signal measured at 5 Hz using a cantilever with a spring constant of 40 N / m is generally less than 10 V. If the balance of the characteristics of the adhesive is considered, it is preferably 5 V or less.

The frictional force of the adhesive layer after photo-hardening at a frequency of 5 Hz is preferably 1.5 times or more, more preferably 2 times or more, and more preferably 2.5 of the frictional force of the adhesive layer before photo-hardening at a frequency of 5 Hz. More than 3 times, especially preferably 3 times or more. The larger the ratio of the friction force before and after the light hardening, the higher the increase rate of the adhesion force generated by the light hardening. The friction force after light curing is generally 20 times or less, preferably 10 times or less, the friction force before light curing.

In addition, the frictional force of the adhesive layer before and after light hardening at frequencies of 0.1 Hz and 5 Hz is due to the FFM mode of a scanning probe microscope ("AFM5300E" manufactured by Hitachi High-Tech Science). Under the following conditions, the friction measurement was performed with a unidirectional scanning width of 5 μm (reciprocating scanning 10 μm), and the differential voltage at a position of 3 μm from the left side of the measurement range was measured and measured.
(Measurement conditions)
Cantilever: "Tap300E-G" manufactured by BudgetSensors (equivalent to spring constant 40 N / m)
ADD value: 8.44 V, DIF value: 0.4 V, FFM value: 0 V
Environment: Vacuum, room temperature Scanning speed: 0.1 Hz, 1 Hz and 5 Hz

Examples of the active light that can be used for photocuring of the adhesive layer (2) include ultraviolet (UV), visible light, infrared, X-ray, α-ray, β-ray, and γ-ray. In terms of easiness in suppressing hardening and hardening of the adhesive layer in the storage state, UV is preferred as the active light. The irradiation intensity or irradiation time of the active light may be appropriately set according to the composition or thickness of the adhesive layer.

The adhesive layer (2) is photocurable, and the timing of curing can be arbitrarily set. Therefore, after the adhesive sheet is attached to the adherend, the partial removal step can be performed at any time during the period before the adhesive is light-cured, and the preparation time of the device manufacturing step can be flexibly handled.

＜ Structure of Adhesive Sheet ＞
The thickness of the adhesive sheet used in the manufacturing method disclosed herein is not particularly limited, and may be, for example, about 3 μm to 11 mm. From the viewpoints of the operability of the adhesive sheet, the thickness of the adhesive sheet is usually preferably 5 μm or more, may be 10 μm or more, and may be 30 μm or more. From the viewpoints of peeling workability of the second region in the partial removal step, in several aspects, an adhesive sheet having a thickness of 50 μm or more, 70 μm or more, or 90 μm or more can be used favorably. From the viewpoints of cutting processability in the cutting step or peeling workability in the second region in the partial removal step, the thickness of the adhesive sheet may be, for example, 1,000 μm or less, 600 μm or less, and 350. μm or less, 200 μm or less, or 150 μm or less.

In the adhesive sheet including the base material layer and the adhesive layer, the thickness of the adhesive layer is not particularly limited, and may be, for example, in a range of about 1 μm to 1000 μm. In several aspects, the thickness of the adhesive layer can be, for example, 3 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 13 μm or more, or 20 μm or more. More than 20 μm. By increasing the thickness of the adhesive layer, the adhesive force after the step of increasing the adhesive force is increased, and there is a tendency that the adhesive sheet is more firmly joined to the laminated body of the adherend. On the other hand, if the thickness of the adhesive layer is too large, there may be workability in the local removal step due to the adhesion between the adhesive in the first region and the adhesive in the second region (such as the first region and the second region). Regional separation) tends to decrease. From this viewpoint, the thickness of the 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, and may be It is 40 μm or less, and may be 30 μm or less.

In the adhesive sheet including the base material layer and the adhesive layer, the thickness of the base material layer is not particularly limited, and may be, for example, about 2 μm to 10 mm. From the viewpoint of the operability of the adhesive sheet or the prevention of cracking of the second region in the partial removal step, the thickness of the base material layer may be, for example, 5 μm or more and 10 μm or more in several aspects. It is 25 μm or more, 35 μm or more, 50 μm or more, and 60 μm or more. From the viewpoint of cutting processability in the cutting step, in some aspects, the thickness of the base material layer may be, for example, 1,000 μm or less, 500 μm or less, 300 μm or less, and 200 μm or less. It can be 150 μm or less, 100 μm or less, or 90 μm or less.

The adhesive sheet used in the manufacturing method disclosed herein can be implemented well in a state where the thickness Ts of the substrate layer is greater than the thickness Ta of the adhesive layer. That is, Ts / Ta is preferably greater than 1. Ts / Ta may be, for example, 1.1 or more, 1.2 or more, 1.5 or more, 2 or more, and 2.5 or more, but it is not particularly limited. The Ts / Ta may be, for example, 50 or less, 20 or less, 10 or less, or 7 or less. By using an adhesive sheet having a composition that satisfies any one of the above upper limit values and / or any one of the above lower limit values, a good balance can be achieved at the same time to achieve good peeling workability in the local removal step and adhesion improvement step. The tendency of the adhesive sheet to adhere firmly to the adherend.

In several aspects, the adhesive sheet used in the attaching step may be, for example, an area of 2500 cm ² or more and a length of the short side of 50 cm or more. In the case of using the large-sized adhesive sheet as described above, it is particularly meaningful to adopt the manufacturing method disclosed herein. By using this adhesive sheet, there is a tendency that one or two or more effects such as improvement in position accuracy, shape accuracy, productivity, and the like are favorably exhibited. In addition, according to the manufacturing method disclosed herein, the partial removal step of peeling and removing the second region of the adhesive sheet is performed before the adhesive force increasing step of increasing the adhesive force of the adhesive sheet, so even with the large size as described above It is also easy to peel and remove the second region of the adhesive sheet. According to the aspect that the area of the above-mentioned adhesive sheet is 3600 cm ² or more, and more preferably 4900 cm ² or more, or that the length of the short side is 60 cm or more, and more preferably 70 cm or more, a higher performance can be achieved. effect.

＜ Applications ＞
According to the method disclosed herein, it is possible to efficiently manufacture a laminated body having a pattern on which an adhesive sheet is formed on an adherend with high accuracy and excellent durability of the pattern. Using this advantage, the method disclosed here can be well applied to the manufacture of building materials such as vehicle exterior materials or interior materials, building exterior materials or interior materials, window glass, kanbans, signs, home appliances, optical A product such as a product, an electronic product, or a component thereof is used as an adherend, and the laminated body of such an adherend is partially covered with a pattern of an adhesive sheet. The laminated body may be the above-mentioned various products or its constituent members. The above-mentioned adhesive sheet is included in various products as a constituent element of the laminated body, and can contribute to giving decoration, display, protection, or the like to the adherend contained in the laminated body, or the article or the member including the laminated body, Reinforcement, shock mitigation, stress concentration mitigation, shape maintenance, shape recovery and other functions. The method disclosed herein can be well applied to, for example, the production of FPC with a film cover layer.

In addition, regarding optical components used for optical products or electronic components used in electronic products, the integration of height, miniaturization, weight reduction, and thinness are continuously developed, and a plurality of thinner optical components having different linear expansion coefficients or thicknesses can be laminated. / Electronic components. By using such a component as an adherend and using the method disclosed herein to form a laminated body in which the component is partially covered by the adhesive sheet, it is possible to impart appropriate rigidity to the optical component / electronic component. Therefore, in the manufacturing process and / or the manufactured product, curling or bending caused by the stress that may be generated between the plurality of members having different linear expansion coefficients or thicknesses can be suppressed.

In addition, in the manufacturing process of optical products / electronic products, when a thin optical member / electronic member is subjected to shape processing such as cutting processing as described above, the member (adhered body) is formed by adhesion. The laminated body partially covered by the sheet, and the above-mentioned adhesive sheet can be used as a reinforcing member to alleviate the local stress concentration of the optical member / electronic member accompanying the processing of the laminated body, which can reduce cracks, cracks, and peeling of the laminated member, etc. risk. The operation of attaching the reinforcing member to the optical member / electronic member can also help to alleviate the local stress concentration of the member during transportation, lamination, rotation, etc., or the bending or bending caused by the weight of the member. Suppression, etc.

Furthermore, devices such as optical products or electronic products including laminated bodies that are partially covered by the pattern of the above-mentioned adhesive sheet by the adherent are at the stage of being available to consumers in the market, even when the device is dropped and placed on a heavy object. In cases where unexpected stress is applied, such as in the following situations, or when flying objects collide, the above-mentioned adhesive sheet contained in the device can be used as a reinforcing member to reduce the stress applied to the device and improve Durability.

The method disclosed here can be used, for example, to make a laminated body that uses the components of various portable devices (portable devices) as adherends and uses the pattern of the adhesive sheet to locally cover the components. The term “carrying” here does not only mean that it can be carried, but refers to the degree of portability that an individual (standard adult) can carry relatively easily. Examples of so-called portable devices include: mobile phones, smart phones, tablet personal computers, notebook personal computers, various portable devices, digital cameras, digital video cameras, and audio equipment (carrying music players) , Recording pen, etc.), computers (calculators, etc.), portable gaming devices, electronic dictionaries, electronic notebooks, electronic books, in-vehicle information equipment, portable radios, portable TVs, portable printers, portable scanning Instruments, portable modems, and other portable electronic devices. In addition, they can also include mechanical watches or pocket watches, flashlights, magnifiers, etc. Examples of the components constituting the above-mentioned portable electronic device may include an optical film or a display panel used in 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 also be well applied to the use of various components in automobiles, home appliances, etc. as adherends, and the use of the pattern of the adhesive sheet to partially cover the laminated body of the components.
[Example]

Hereinafter, several embodiments of the present invention will be described, but it is not intended to limit the present invention to those shown in the specific examples. In addition, "part" and "%" in the following descriptions are based on weight unless otherwise specified.

(Preparation of polymer A1)
In a reaction vessel equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooler, 63 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of N-vinylpyrrolidone (NVP), and methyl methacrylate were added. (MMA) 9 parts, 2-hydroxyethyl acrylate (HEA) 13 parts, and 200 parts of ethyl acetate as a polymerization solvent. After stirring at 60 ° C under a nitrogen atmosphere for 2 hours, put them in as a thermal initiator. 0.2 parts of AIBN was reacted at 60 ° C for 6 hours to obtain a solution of polymer A1. The Mw of the polymer A1 was 1.1 million.

(Preparation of polymer A2)
Except changing the composition of the monomers used to 2EHA / HEA = 95/5 (weight ratio), solution polymerization was performed in the same manner as in the synthesis of polymer A1, thereby obtaining a solution of polymer A2. The Mw of the polymer A2 was 900,000.

(Preparation of polymer A3)
In a reaction vessel equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooler, add 96.2 parts of 2EHA, 3.8 parts of HEA, and 150 parts of ethyl acetate as a polymerization solvent, and stir at 60 ° C under a nitrogen environment for 2 hours. 0.2 parts of AIBN as a thermal initiator was added and reacted at 60 ° C. for 6 hours to obtain a solution of polymer A3 (solid content 40%). The Mw of the polymer A3 was 540,000.

(Preparation of polymer B1)
In a reaction vessel equipped with a stirring wing, a thermometer, a nitrogen introduction tube and a cooler, put 40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), 20 parts of 2-ethylhexyl methacrylate (2EHMA), 9 parts of a polyorganosiloxane skeleton-containing methacrylate monomer (brand name: X-22-174ASX, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) having a functional group equivalent of 900 g / mol and a functional group equivalent of 4600 g 11 parts per mol of a polyorganosiloxane-containing methacrylate monomer (trade name: KF-2012, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 100 parts of ethyl acetate, and thioglycerin as a chain transfer agent 0.6 parts, after stirring at 70 ° C for 1 hour under a nitrogen atmosphere, 0.2 parts of AIBN as a thermal initiator was added, and after reacting at 70 ° C for 3 hours, 0.1 parts by weight of AIBN was further added, followed by 80 ° C The reaction was continued for 5 hours. In this way, a solution of a polymer B1 containing a siloxane structure was obtained. The Mw of the polymer B1 was 20,000.

The weight-average molecular weight of each of the polymers was measured using a GPC apparatus (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and was determined by polystyrene conversion.
・ Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
・ Sample injection volume: 10 μl
・ Eluent: THF ・ Flow rate: 0.6 ml / min
・ Measurement temperature: 40 ° C
・ Pipe:
Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
Reference column; TSKgel SuperH-RC (1)
・ Detector: Differential refractometer (RI)

＜ Production of adhesive sheet ＞
(Adhesive sheet D1)
In the solution of the polymer A1 described above, 2.5 parts of polymer B1 and 2.5 parts of an isocyanate-based cross-linking agent (trade name: Takenate) were added based on the solid content of 100 parts of the polymer A1 contained in the solution. D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd.) was uniformly mixed to prepare an adhesive composition C1.
Adhesive composition C1 was directly coated on one side of a 75 μm-thick PET film (“Lumirror S10” manufactured by Toray) without surface treatment, and dried at 110 ° C. for 2 minutes to form a thickness of 25 μm. Adhesive layer, the release layer (MRQ50T100 manufactured by Mitsubishi Chemical Co., polyester film treated with silicone release agent on one side, thickness 50 μm) is attached to the surface (adhesive surface) of the adhesive layer. Treat the surface for protection. In this way, an adhesive sheet D1 was obtained in the form of having an adhesive layer on one side of a substrate layer including a PET film having a thickness of 75 μm, and the surface (adhesive surface) of the adhesive layer was protected by a release liner.

(Adhesive sheet D2)
In the solution of the polymer A1 described above, an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropanebenzene) was added based on the solid content based on 100 parts of the polymer A1 contained in the solution. 2.5 parts of dimethyl diisocyanate, manufactured by Mitsui Chemicals Co., Ltd., light hardener (trade name: A-200, polyethylene glycol # 200 diacrylate, functional group equivalent 154 g / eq, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 30 Parts and 0.1 parts of the photoinitiator were mixed uniformly to prepare an adhesive composition C2. As a photoinitiator, 1-hydroxycyclohexylacetophenone ("Irgacure 184" manufactured by BASF) was used.
On one side of a 75 μm-thick PET film ("Lumirror S10" manufactured by Toray) without surface treatment, the adhesive composition C2 was directly applied using a grooved roller, and dried at 130 ° C for 1 minute, thereby drying A 25 μm thick adhesive layer was formed. On the surface (adhesive surface) of the adhesive layer, a release-treated surface (a PET film treated with a silicone release agent, a thickness of 25 μm) is bonded to the release-treated surface for protection, and the protection is performed at 25 ° C for 4 days. Cross-linking by aging treatment. In this way, an adhesive sheet D2 in a form where the adhesive surface is protected by a release liner is obtained.

(Adhesive sheet D3)
In the solution of the polymer A2 described above, an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropanebenzene) was added based on the solid content based on 100 parts of the polymer A2 contained in the solution. 2.5 parts of dimethyl diisocyanate, manufactured by Mitsui Chemicals Co., Ltd., were mixed uniformly to prepare an adhesive composition C3. In addition to using the adhesive composition C3 instead of the adhesive composition C1, an adhesive sheet D3 in a form where the adhesive surface is protected by a release liner is obtained in the same manner as the production of the adhesive sheet D1.

(Adhesive sheet D4)
Except that the polymer B1 was not used, an adhesive composition C4 was prepared in the same manner as in the preparation of the adhesive composition C1. In addition to using the adhesive composition C4 instead of the adhesive composition C1, an adhesive sheet D4 in a form where the adhesive surface is protected by a release liner is obtained in the same manner as the production of the adhesive sheet D1.

(Adhesive sheet D5)
In the solution of the polymer A3, 2.5 parts of polymer B1 and an isocyanate-based crosslinking agent (trade name: Coronate L ( 3.3 parts of 75% ethyl acetate solution of trimethylolpropane / toluene diisocyanate terpolymer adduct, manufactured by Tosoh Company), uniformly mixed to prepare adhesive composition C5. Adhesive composition C5 was used instead of the adhesive Except for the composition C1, an adhesive sheet D5 having an adhesive surface protected by a release liner was obtained in the same manner as in the production of the adhesive sheet D1.

＜ Measurement of adhesion to polyimide ＞
A 12.5 μm-thick polyimide film ("Kapton 50EN" manufactured by Toray-Dupont) was fixed to a glass plate through a double-sided adhesive tape ("No. 531" manufactured by Nitto Denko) to prepare an adhesive force measurement. Audition. In addition, the adhesive sheets D1 to D4 and D5 were cut into short strips having a width of 25 mm to prepare samples for measurement.
Under a standard environment of 23 ° C. and 50% RH, a 2 kg roller was reciprocated once, and the adhesive surface of the measurement sample was crimped to the test piece. After leaving it in the above standard environment for 30 minutes, it was measured using a tensile tester ("TCM-1kNB" manufactured by Minebea) in accordance with JIS Z0237 under conditions of a peeling angle of 180 degrees and a tensile speed of 300 mm / min. Peeling strength (initial adhesion) B ₀ [N / 25 mm].

Further, the adhesive sheet for D1, D2, D5, and the initial adhesive force B by the same manner as the measurement of the _0-pressure measurement of the contact adhesive surface of the sample to the test strip, which will be placed for 30 minutes under the above standard environment, After applying the stimulus shown in Table 1 and leaving it in the standard environment for 30 minutes, the peeling strength (adhesive strength after stimulation) B ₁ was measured under the conditions of a peeling angle of 180 degrees and a tensile speed of 300 mm / min. N / 25 mm]. The contents of each stimulus shown in Table 1 are specifically described below.
Heating: heating at 80 ° C for 5 minutes.
UV irradiation: The UniField manufactured by Ushio company was used to irradiate ultraviolet rays with a main wavelength of about 365 nm in a light amount of 2000 mJ / cm ² .

From the obtained results, the adhesion increase ratio (B ₁ / B ₀ ) was calculated as the ratio of the adhesion B ₁ to the initial adhesion B ₀ after stimulation. The results are shown in Table 1. Furthermore, the measurement sample was pressure-bonded to the test piece, and after being left in the standard environment for 24 hours, the peeling strength was measured at a peeling angle of 180 degrees and a tensile speed of 300 mm / min without applying a special stimulus (24 Adhesion after hours), the result is that the adhesive sheet D1 is 0.45 N / 25 mm, the adhesive sheet D2 is 0.56 N / 25 mm, the adhesive sheet D3 is 0.36 N / 25 mm, and the adhesive sheet D4 is 19.29 N / 25 mm , The adhesive sheet D5 is 0.77 N / 25 mm, both of which are less than 1.6 times the initial adhesive force B ₀ .

[Table 1]

＜ Manufacturing of laminated body ＞
(Manufacturing example 1)
The adhesive sheet D1 was cut into a width of 25 mm and a length of 100 mm to prepare an adhesive sheet for manufacturing a laminated body. In addition, a polyimide film ("Kapton 50EN" manufactured by Toray-Dupont, Inc.) having a thickness of 12.5 μm, a width of 30 mm, and a length of 120 mm was prepared as an adherend. The adhesive sheet is adhered to the adherend, and the adhesive sheet is subjected to pattern processing to give stimulation to increase the adhesive force, thereby producing a structure in which the pattern-processed adhesive sheet is used to cover the adherend. Laminated body.

Specifically, the center of the adherend is aligned with the center of the adhesive sheet, and the adhesive sheet is attached to the adherend using a hand pressure roller (attachment step).
The center of the width of the adhesive sheet in the obtained adhesive sheet / adhered volume layer is set from one end in the longitudinal direction of the adhesive sheet to a straight line extending to the other end with a width of 2 mm and a second length of 100 mm. region. A laser beam is irradiated from the adhesive sheet surface side along the boundary (two straight lines) of the second region and the first region on both sides of the adhesive sheet to perform a cutting process (cutting step) of cutting only the adhesive sheet D1. The above cutting process is performed using a laser cutting device "Spirit, Model number SI-30V" manufactured by GCC, under the following conditions.
Speed: 9.0%
Power: 10.0%
DPI: 500
PPI: 400
One end of the second region was peeled off from the adherend, clamped by a chuck of a tensile tester, and stretched in the length direction of the adhesive sheet under the conditions of a peeling angle of 180 degrees and a stretching speed of 300 mm / min. Therefore, the slit-shaped second region with a width of 2 mm is peeled off from the adherend (partial removal step).
Then, the above-mentioned heating (80 ° C., 5 minutes) was performed as an adhesion increase stimulus (adhesion increase step) to produce a target laminate.

(Manufacturing example 2)
Use the adhesive sheet D2 instead of the adhesive sheet D1, and change the applied stimulus self-heating to the above-mentioned UV irradiation (principal wavelength of about 365 nm and light intensity of 2000 mJ / cm ² ) in the step of increasing the adhesive force. In addition to the above, The laminated body was produced by the same procedure as in Production Example 1.

(Production Examples 3 to 5)
A laminated body was produced by the same procedure as in Production Example 1 except that the adhesive force raising step was not performed using the adhesive sheets D1, D3, and D4, respectively.

(Manufacturing example 8)
A laminated body was produced by the same procedure as in Production Example 1 except that the adhesive sheet D5 was used instead of the adhesive sheet D1.

(Evaluation of Removability of Slit Part)
In the partial removal step of each manufacturing example, when no deformation such as elongation of the adherend was found when the adherend was peeled from the second region, it was evaluated as "G" (good pattern workability), and when deformation was found At that time, it was evaluated as "P" (pattern workability was insufficient). The results are shown in Table 2.
Furthermore, in Production Example 5, the peeling of the second region could not be properly performed, so the following durability test was not performed. In addition, in Production Examples 1 to 4, and 8 even when the second region was peeled off, no paste remained in the adherend.

(Durability test)
For the laminated bodies obtained in Manufacturing Examples 1 to 4, and 8, a flat body no-load U-shaped telescopic tester "DLDM111LH" and a jig (flat body no-load U-shaped telescopic test fixture) manufactured by Yuasa system were used. The durability test was performed under the conditions of a telescopic speed of 30 rpm, a bending radius of 3 mm, and a number of telescopic times.
Specifically, as shown in FIG. 6, both ends x and y of the sample 60 are fixed to the splint portions 61 and 62 of the testing machine by using a double-sided tape (not shown). The sample 60 was folded in a U-shape with a bending radius of 3 mm from the flat state with the adhesive sheet side as the inner side. When the sample 60 is bent, the two ends x, y of the sample 60 are brought into contact by the action of the splint, and the other parts of the sample 60 are used from the outer sides under the condition of no load by using the additional plate portions 63 and 64. embed.
By visually observing the state of the sample after 100 expansions, it was evaluated as "G" (good durability) when no bulge was found between the adhesive sheet and the adherend, and "P" when it was found. "(Insufficient durability). The results are shown in Table 2.

[Table 2]

As shown in Table 2, in Production Examples 1, 2, and 8 in which the adhesion-rise treatment was performed by heating or UV irradiation, the second region in the partial removal step had good peelability, and the manufactured laminate showed good durability. Sex. Particularly good results were obtained in Production Examples 1 and 2 using the adhesive sheets D1 and D2 having an adhesive layer containing a polymer A1 copolymerized with N-vinyl cyclic amidine. On the other hand, in Manufacturing Examples 3 to 5 which were not subjected to the adhesion-increasing treatment, the laminates obtained in Manufacturing Examples 3 and 4 had low durability, and the peelability of the second region in the partial removal step in Manufacturing Example 5 was low. There is a problem.

(Manufacturing example 6)
As shown in FIG. 7, the width center of one side of the polyimide film 72 having a width of 120 mm and a length of 220 mm has a width of 1.9 mm extending linearly from one end in the length direction of the film 72 to the other end. The adherend 70 of the copper pattern wiring 74. The adhesive sheet D1 is cut into a width of 100 mm and a length of 200 mm, and the obtained adhesive sheet is attached to the approximate center of the copper pattern wiring forming surface of the adherend 70 by a hand roller (attachment step). .
A second region with a width of 2 mm extending across the adhesive sheet in the width direction is set on the obtained adhesive sheet / adhered volume layer to overlap the copper pattern wiring, along the second region and both sides thereof The boundary of the first region is subjected to laser cutting similar to that of Production Example 1 from the adhesive sheet side of the laminate, thereby performing a cutting process (cutting step) of cutting only the adhesive sheet.
Then, by peeling and removing the second area from the adherend (partial removal step), it is obtained that the adherend is partially covered by the adhesive sheet having a slit with a width of 2 mm, and the copper pattern wiring is exposed in the slit. Laminated body.

(Manufacturing example 7)
The adhesive sheet D4 was cut to a width of 100 mm and a length of 200 mm, and the back surface (the surface of the base material layer opposite to the side on which the adhesive layer was provided) was stuck to a temporary fixing tape manufactured by Toyochem. LE-900 "adhesive surface.
On the obtained adhesive sheet / temporary fixing tape laminate, set a second region with a width of 2 mm extending across the adhesive sheet in the width direction, along the boundary between the second region and the first regions on both sides of the adhesive sheet, The same laser cutting as in Production Example 1 was performed from the adhesive sheet side of the laminate, thereby performing a cutting process of cutting only the adhesive sheet.
Then, the second region is peeled and removed from the temporary fixing tape to obtain a laminate on which the back surface of the adhesive sheet having the slits formed therein is supported by the temporary fixing tape.
Using a high-precision film bonding machine (model: BCF250RH) manufactured by Beac Company, the adhesive side of the laminate was crimped to the same blanket as in Manufacturing Example 6 at room temperature in such a manner that the slits overlap the copper pattern wiring. After the adherend, only the temporary fixing tape described above was peeled off.

(Slit formation accuracy evaluation test)
For the multilayer bodies obtained in Manufacturing Examples 6 and 7, a length measuring microscope (model: STM6) manufactured by Olympus was used. As shown in FIG. 8, the center line L0 of the copper pattern wiring 74 and the adhesive sheet 76, The distance of the center line L1 of the slits between 76 is measured as the error X. Based on this measurement result, it is judged as "Pass" when the error X is less than 50 μm, and it is judged as "Fail" when the error X is 50 μm or more. The results are shown in Table 3.

[table 3]

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

1‧‧‧ laminated body

10‧‧‧ adherend

10A‧‧‧ surface

20‧‧‧ Adhesive sheet

21‧‧‧First Zone

21A‧‧‧Adhesive sheet

21B‧‧‧Adhesive sheet

22‧‧‧Second Zone

50‧‧‧Laminated body manufacturing device

51‧‧‧ Attachment

52‧‧‧cutting mechanism

53‧‧‧Stripping agency

54‧‧‧Adhesive force rising mechanism

60‧‧‧sample

61‧‧‧Plywood section

62‧‧‧Plywood section

63‧‧‧ Board

64‧‧‧ Board

70‧‧‧ adherend

72‧‧‧Polyimide film

74‧‧‧ copper pattern wiring

76‧‧‧ Adhesive sheet

202‧‧‧ substrate layer

204‧‧‧Adhesive layer

C‧‧‧ cut off the planned line

L‧‧‧ laser light

L0‧‧‧ Centerline of copper pattern wiring

L1‧‧‧ the centerline of the slit

S10‧‧‧ Attach step

S20‧‧‧ Cutting steps

S30‧‧‧Partial removal step

S40‧‧‧Adhesion step

X‧‧‧ error

x‧‧‧ end

y‧‧‧end

FIG. 1 is a flowchart showing a method for manufacturing a laminated body according to an embodiment.

FIG. 2 is a perspective view showing a laminated body manufactured by a laminated body manufacturing method according to an embodiment.

FIG. 3 is a sectional view taken along the line III-III in FIG. 2.

FIG. 4 is a perspective view illustrating a cutting step of a method for manufacturing a laminated body according to an embodiment.

5 is an explanatory diagram showing a schematic configuration of a multilayer body manufacturing apparatus used in a multilayer body manufacturing method according to an embodiment.

FIG. 6 is an explanatory diagram showing a method for implementing a durability test.

FIG. 7 is a plan view showing an adherend used in a slit formation accuracy evaluation test.

FIG. 8 is an explanatory diagram showing an error X in a slit formation accuracy evaluation test.

Claims (14)

A laminated body manufacturing method. The laminated system includes an adherend and an adhesive sheet partially covering the adherend, and the manufacturing method of the laminated body includes: The attaching step includes attaching an adhesive sheet including a substrate layer and an adhesive layer laminated on at least the surface of the adherend side of the substrate layer to the adherend; The cutting step includes cutting the boundary between the first region constituting the adhesive sheet and the second region not constituting the adhesive sheet in the adhesive sheet; A partial removal step, which leaves the first region on the adherend and peels and removes the second region from the adherend; and The step of increasing the adhesive force is to increase the adhesive force of the first region to the adherend. The method for manufacturing a laminated body according to claim 1, wherein the step of increasing the adhesive force includes heat treatment. For example, the method for manufacturing a laminated body according to claim 2, wherein the adhesive layer contains: polymer A, whose glass transition temperature is less than 0 ° C; and polymer B, which is a monomer having a polyorganosiloxane frame and (A Based) a copolymer of acrylic monomers. The method for producing a laminated body according to claim 3, wherein the monomer component constituting the polymer A contains N-vinyl cyclic amidine. The method for manufacturing a laminated body according to claim 1, wherein the step of increasing the adhesive force includes an ultraviolet irradiation treatment. The method for manufacturing a laminated body according to claim 5, wherein the adhesive layer comprises a photocurable composition containing a base polymer and a photohardener, The photocuring agent is a polyfunctional (meth) acrylate, and The content of the photocuring agent is 1 part by weight or more and 50 parts by weight or less based on 100 parts by weight of the base polymer. The method for manufacturing a laminated body according to any one of claims 1 to 6, wherein in the step of increasing the adhesive force, the adhesive force of the adhesive sheet to the adherend is increased to more than twice that before the step. The method for manufacturing a laminated body according to any one of claims 1 to 7, wherein the partial removing step is performed before the adhesive force of the adhesive sheet to the adherend exceeds 2 N / 25 mm. The laminated body manufacturing method according to any one of claims 1 to 8, wherein the adhesion force of the adhesive sheet in the first region to the adherend is 3 N / 25 mm or more by the above-mentioned adhesive force increasing step. The laminated body manufacturing method according to any one of claims 1 to 9, wherein the second region is set so that at least one end of the second region reaches the end of the adhesive sheet. The method for manufacturing a laminated body according to claim 10, wherein the second region has a shape that reaches one end of the adhesive sheet and widens toward the end of the adhesive sheet. The laminated body manufacturing method according to any one of claims 1 to 11, wherein the area of the above-mentioned adhesive sheet used in the above-mentioned attaching step is 2500 cm ² or more, and the length of the short side is 50 cm or more. The method for manufacturing a laminated body according to any one of claims 1 to 12, wherein the adhesive sheet and the adherend used in the above-mentioned attaching step include a plurality of units corresponding to the laminated body; and As a step performed after the above-mentioned attaching step, a step of dividing the adhesive sheet and the adherend into the units is further included. A laminated body manufacturing device is a device for implementing the manufacturing method according to any one of claims 1 to 13, and includes: An attachment mechanism for attaching the above-mentioned adhesive sheet; A cutting mechanism for cutting the adhesive sheet; A peeling mechanism that peels the second region of the adhesive sheet; and The adhesive force increasing mechanism imparts an adhesive force increasing stimulus to the adhesive sheet.