KR20190132531A - Manufacturing method of laminate - Google Patents

Abstract

A method for producing a laminate comprising an adherend and an adhesive piece partially covering the adherend, wherein the adhesive force of the adhesive piece to the adherend is 5 N / 25 mm or more. The laminated body manufacturing method is a cutting process which affixes an adhesive sheet to the said to-be-adhered body, and a cutting process to the boundary of the 1st area which comprises the said adhesive piece among the said adhesive sheets, and the 2nd area | region which does not comprise the said adhesive piece. And a partial removing step of peeling and removing the second region from the adherend while leaving the first region on the adherend. Here, the said adhesive layer contains the polymer A which is less than 0 degreeC, and polymer A which contains N-vinyl cyclic amide in a structural monomer component, and the copolymer B of the monomer which has a polyorganosiloxane skeleton, and a (meth) acrylic-type monomer. And the said partial removal process is performed before the adhesive force with respect to the to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm.

Description

Manufacturing method of laminate

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

This application claims the priority based on Japanese Patent Application 2017-253311 for which it applied on December 28, 2017, and Japanese Patent Application 2018-228925 for which it applied on December 6, 2018, and the full content of those applications Is incorporated herein by reference.

According to the laminated body which partially covered the to-be-adhered body with the said adhesive piece by sticking 1 or 2 or more adhesive pieces to a to-be-adhered body, various patterns can be expressed according to the external shape and arrangement | positioning of the said adhesive. Thus, as a method of manufacturing the laminated body which the to-be-adhered body partially covered with the adhesive piece with high precision, the adhesive sheet is previously cut into the shape of the desired adhesive piece like the coverlay film bonding of a circuit board, for example, and the adhesive piece is a to-be-adhered body. The method of aligning and sticking in the position is generally used. Patent document 1 is mentioned as a technical document regarding this kind of technology.

Japanese Patent Application Publication No. 2013-38379

However, in the method mentioned above, since an adhesive sheet is cut in advance in the shape of a desired adhesive piece, and it positionally arranges and joins to a predetermined to-be-adhered part site | part, the error of both cut precision and joining precision arises. For this reason, in order to manufacture a product with high yield in manufacture of the electronic component to be miniaturized and a high definition in future, it is feared that very expensive installation will be needed. In addition, when the size of the cut adhesive piece is large or the shape is complicated, for example, it may become more difficult to affix the adhesive piece to the adherend with high positional accuracy and shape accuracy. In particular, in the case where a strongly adhesive pressure sensitive adhesive piece is used to produce a durable laminate, there is a tendency that the difficulty of an operation of accurately attaching the pressure sensitive adhesive piece to the adherend increases.

Then, an object of this invention is to provide the method of efficiently manufacturing the laminated body in which the pattern by an adhesive piece was formed with high precision on a to-be-adhered body, and the said adhesive piece was firmly bonded to the to-be-adhered body. Another related invention is to provide a device suitable for the practice of this manufacturing method.

By this specification, the manufacturing method of the laminated body which includes an adherend and the adhesive piece which partially covers this to-be-adhered body, and whose adhesive force with respect to the to-be-adhered body of the said adhesive piece is 5N / 25mm or more is provided. The laminated body manufacturing method includes a sticking step of affixing a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface on the adherend side of the base material layer to the adherend, and the pressure-sensitive adhesive piece in the pressure-sensitive adhesive sheet. A cut process of performing a cutting process at a boundary between a first region to be configured and a second region not forming the adhesive piece, and peeling the second region from the adherend while leaving the first region on the adherend. Some removal processes for removal are included in this order. Here, the said partial removal process is performed before the adhesive force with respect to the to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm.

According to the said manufacturing method, by implementing the said sticking process, the said cutting process, and the said partial removal process in this order, the structure by which the 1st area | region was arrange | positioned on a to-be-adhered body with shape precision and a position high precision can be obtained efficiently. Moreover, since the said partial removal process is performed before the adhesive force with respect to the said to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm, it is easy to perform the operation which peels a 2nd area | region from the to-be-adhered body, and also the deformation | transformation and damage of an to-be-adhered body It is difficult to occur.

In some embodiments, after bonding to a polyimide, the adhesive force after 24 hours passing at 23 degreeC can use preferably 2 N / 25mm or less as said adhesive sheet. According to such an adhesive sheet, it can respond flexibly to the lead time of the manufacturing process of a laminated body.

In some aspects of the laminated body manufacturing method disclosed here, heat processing is performed after the said partial removal process, and the adhesive force with respect to the to-be-adhered body of a said 1st area | region is made into 5 N / 25 mm or more. This aspect uses the adhesive sheet provided with the adhesive layer containing the polymer A which is a copolymer of the monomer which has a polyorganosiloxane frame | skeleton, and a (meth) acrylic-type monomer, for example with a glass transition temperature of less than 0 degreeC. Although it can implement, it is not limited to this.

In some embodiments, the monomer component constituting the polymer A may include an N-vinyl cyclic amide. Thus, since the adhesive sheet using the polymer A of the composition containing N-vinyl cyclic amide as a structural monomer component can exhibit favorable adhesive strength synergism, it can be used suitably for implementation of the manufacturing method disclosed here.

According to this specification, it is a manufacturing method of the laminated body containing the to-be-adhered body and the to-be-adhered body, and the adhesive force with respect to the to-be-adhered body of the said adhesion piece is 5 N / 25mm or more,

A sticking step of attaching a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface on the adherend side of the base material layer to the adherend;

A cutting step of performing a cutting process on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece of the adhesive sheet; And,

A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;

, In this order,

Here, the said adhesive layer contains Polymer A which is a copolymer of the polymer A whose glass transition temperature is less than 0 degreeC, the monomer which has a polyorganosiloxane skeleton, and a (meth) acrylic-type monomer,

The monomer component constituting the polymer A contains N-vinyl cyclic amide,

The said partial removal process is performed before the adhesive force with respect to the to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm,

The laminated body manufacturing method which heat-processes after the said partial removal process and makes the adhesive force with respect to the to-be-adhered body of a said 1st area | region to 5 N / 25mm or more is provided. According to this method, the laminated body in which the pattern by an adhesive piece was formed with high precision on a to-be-adhered body can be manufactured efficiently.

In some embodiments, the monomer component constituting the polymer A may further include a hydroxyl group-containing monomer in addition to the N-vinyl cyclic amide. The manufacturing method disclosed here can be suitably performed using the adhesive sheet which used the polymer A of the composition combining N-vinyl cyclic amide and a hydroxyl-containing monomer as a structural monomer component in this way.

In some other aspect of the laminated body manufacturing method disclosed here, an ultraviolet irradiation process is performed after the said partial removal process, and the adhesive force with respect to the to-be-adhered body of a said 1st area | region is made into 5 N / 25 mm or more. This aspect consists of a photocurable composition containing a base polymer and a photocuring agent, for example, The said photocuring agent is polyfunctional (meth) acrylate, and content of the said photocuring agent is 1 with respect to 100 weight part of said base polymers. Although it can carry out using the adhesive sheet provided with the adhesive layer which is a weight part or more and 50 weight part or less, it is not limited to this.

In addition, you may implement the laminated body manufacturing method disclosed here in the aspect which keeps at normal temperature until the adhesive force with respect to the to-be-adhered body of a said 1st area | region becomes 5 N / 25 mm or more after the said partial removal process.

In addition, in this specification, normal temperature means the temperature of about 0 degreeC-35 degreeC, typically 10 degreeC-35 degreeC, unless it mentions specially.

In some aspects, as said adhesive sheet, thickness is 30 micrometers or more, and the thing of thickness Ts of the said base material layer being 2 times or more of the thickness Ta of the said adhesive layer can be used preferably. By using such an adhesive sheet, the advantage that it is easy to perform a sticking operation to a to-be-adhered body, and peeling operation of a 2nd area is acquired.

It is preferable that the said 2nd area | region is set so that the at least one end may reach the end of the said adhesive sheet. Thereby, the advantage that it is easy to pick up a 2nd area at the time of performing said partial removal process is acquired. The second region may have a shape in which one end leading to the end of the pressure-sensitive adhesive sheet becomes wider toward the end of the pressure-sensitive adhesive sheet from the viewpoint of improving pickup performance.

The manufacturing method disclosed here can be preferably performed in the aspect which uses the adhesive sheet whose area is 2500 cm <2> or more and the length of a short side is 50 cm or more for the said pasting process. In the aspect using an adhesive sheet having such a large area and a wide width, the advantages of employing the manufacturing method disclosed herein can be more effectively exerted.

The manufacturing method disclosed here is a process performed after the said sticking process, using the thing containing two or more units corresponding to the said laminated body as the said adhesive sheet and the to-be-adhered body used for the said sticking process, The said adhesion The method may further include a dividing step of dividing the sheet and the adherend into the unit. Thus, a plurality of laminated bodies can be manufactured efficiently by dividing the adhesive sheet containing a some unit after attaching to a to-be-adhered body. In addition, the structure of the said some unit may be the same and may differ.

According to this specification, the apparatus for manufacturing the laminated body containing a to-be-adhered body and the adhesive piece partially laminated | stacked on this to-be-adhered body is provided. The apparatus includes a sticking mechanism for affixing an adhesive sheet. In addition, the apparatus may include a cut mechanism for cutting the adhesive sheet. In addition, the apparatus may include a peeling mechanism for peeling the second region. Using the manufacturing apparatus which has such a structure, any laminated body manufacturing method disclosed here can be implemented suitably.

Moreover, what suitably combined each element mentioned above can also be included in the scope of the invention which seeks protection by a patent by this patent application.

1 is a flowchart showing a laminate manufacturing method according to one embodiment.
FIG. 2 is a perspective view showing a laminate manufactured by the laminate manufacturing method according to the embodiment. FIG.
3 is a cross-sectional view taken along the line III-III of FIG. 2.
4 is a perspective view illustrating a cut step of the laminate manufacturing method according to the embodiment.
FIG. 5: is explanatory drawing which shows schematic structure of the laminated body manufacturing apparatus used for the laminated body manufacturing method which concerns on one Embodiment.
6 is an explanatory diagram showing a method for performing a durability test.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described. Matters other than those specifically mentioned in the present specification and matters necessary for the practice of the present invention may be understood by those skilled in the art based on the teachings on the practice of the invention described herein and the technical common knowledge at the time of filing. This invention can be implemented based on the content disclosed by this specification and technical common sense in the said field | area.

In addition, in the following drawings, the same code | symbol may be attached | subjected and demonstrated to the member and site | part which exhibit the same effect, and the overlapping description may be abbreviate | omitted or simplified. In addition, embodiment described in drawing is typical in order to demonstrate this invention clearly, and does not necessarily show actual size and scale correctly.

<< manufacturing method of laminated body >>

1 is a flowchart illustrating a laminate manufacturing method according to an embodiment, FIG. 2 is a perspective view illustrating a laminate manufactured by the method, and FIG. 3 is a cross-sectional view taken along line III-III thereof. As shown to FIG. 2, 3, the laminated body 1 manufactured by this embodiment is 21 A of adhesive pieces which partially cover the to-be-adhered body 10 and the surface 10A of this to-be-adhered body 10. FIG. , 21B). After sticking the adhesive sheet 20 to the to-be-adhered body 10, the adhesive pieces 21A and 21B leave the 1st area | region 21 on the to-be-adhered body 10 of the said adhesive sheet 20, and a 2nd area | region It is formed from the 1st area | region 21 left on the to-be-adhered body 10 by peeling and removing 22 from the to-be-adhered body 10. FIG. The adhesive sheet 20 has a structure in which the adhesive layer 204 is laminated on one side of the substrate layer 202.

As shown in FIG. 1, the laminated body manufacturing method which concerns on this embodiment includes sticking process S10, cut process S20, and some removal process S30 in this order.

In the sticking step S10, the adhesive sheet 20 is stuck to the adherend 10. The adhesive sheet 20 used in this process is the structure of the 1st area | region 21 which is an area | region contained in the component of the laminated body 1 as adhesive pieces 21A, 21B, and the laminated body 1 The second region 22 is used only in the manufacturing process of the laminate 1 without being an element. In the example shown in FIG. 2, the 2nd area | region 22 extended linearly from one end of the longitudinal direction of the said adhesive sheet 20 to the other end is set in the substantially center of the width | variety of the adhesive sheet 20. FIG. . In the adhesive sheet 20 used for the sticking step S10, the first region 21 and the second region 22 are physically connected, and these regions 21 and 22 are treated as a series of adhesive sheets 20. Can be.

In cut process S20, a cutting process is given to the boundary of the 1st area | region 21 and the 2nd area | region 22 of the adhesive sheet 20 affixed on the to-be-adhered body 10. FIG. For example, as shown in FIG. 4, the laser cutting which irradiates the laser beam L along the cut | disconnection scheduled line C which forms the boundary of the 1st area | region 21 and the 2nd area | region 22 is performed. In addition, although the example of laser cutting is shown in FIG. 4, the means of a cutting process is not specifically limited, It can select from well-known various cutting means suitably according to an objective and a use. Examples of such cutting means include laser cutting using a laser beam such as a CO ₂ laser or a YAG laser; Cutting by blades such as Thomson blades, pinnacle blades, rotary blades, and knives; Blade cutting; Although these etc. are mentioned, It is not limited to these. The cutting means can be used individually by 1 type or in combination of 2 or more types.

In some removal process S30, before the adhesive force with respect to the to-be-adhered body of the adhesive sheet stuck to the to-be-adhered body in a sticking process exceeds 2 N / 25 mm (in other words, after sticking, while adhesive force is suppressed to 2 N / 25 mm or less ) Is performed. In this partial removal process S30, the 2nd area | region 22 is peeled off from the to-be-adhered body 10, leaving the 1st area | region 21 on the to-be-adhered body 10. FIG. For example, the 2nd area | region 22 was dug from the one end of the long side direction of the adhesive sheet 20 toward the other end. Thereby, as shown to FIG. 2, 3, the adhesive pieces 21A and 21B formed from the 1st area | region 21 are arrange | positioned spaced apart from each other on the to-be-adhered body 10, and the adhesive pieces 21A and 21B. A structure in which the adherend 10 is exposed between them is formed.

In the laminated body manufacturing method which concerns on this embodiment, after sticking the adhesive sheet 20 to the to-be-adhered body 10, one part of the said adhesive sheet 20, ie, the 2nd area | region 22, is peeled off from the to-be-adhered body 10. By removing, the coating pattern which consists of two adhesive pieces 21A and 21B spaced apart from each other is formed on the to-be-adhered body 10. FIG. According to this method, the to-be-adhered body 10 is formed in the form of the adhesive sheet 20 of the 1st area | region 21 which comprises two adhesive pieces 21A, 21B spaced apart from each other in the laminated body 1 in the form of one adhesive sheet 20. ), And at the time of sticking the adhesive sheet 20, adjustment of the relative positional relationship between the adhesive piece 21A and the adhesive piece 21B becomes unnecessary, whereby the manufacturing efficiency of the laminate 1 is improved. do. In addition, after the adhesive sheet 20 is affixed to the adherend 10, a cutting process is performed at the boundary between the first region 21 and the second region 22 of the adhesive sheet 20, so that the first region ( It is easy to raise the shape precision of 21) and the position precision with respect to the to-be-adhered body 10. For example, in the sticking process S10, when the some shift | offset | difference generate | occur | produces in the sticking position of the adhesive sheet 20 with respect to the to-be-adhered body 10, a temperature change, a release of internal stress, etc. Even when expansion and contraction occur, the influences thereof can be eliminated or reduced by adjusting the position and shape of the cutting process in the cutting step S20.

In the said manufacturing method, the laminated body 1 whose adhesive force with respect to the to-be-adhered body of adhesive piece 21A, 21B is 5 N / 25mm or more is manufactured. The adhesive pieces 21A and 21B are firmly bonded to the adherend 10 in this way, when the laminate 1 is used, external forces such as human hands contacting, deformation of the adherend, or lamination. It is preferable from the viewpoint of suppressing the idea that the adhesive pieces 21A, 21B peel off or float from the adherend 10 due to environmental factors such as the body being exposed to weather or temperature change. On the other hand, in some removal process S30, when adhesiveness with respect to the to-be-adhered body 10 of the 2nd area | region 22 is too high, deformation | transformation, such as elongation, etc. in the to-be-adhered body 10 at the time of peeling of the 2nd area | region 22, etc. Damage such as peeling may occur, or a problem may occur such that the second region 22 breaks during peeling. According to the said manufacturing method, adhesive piece 21A, 21B is avoided by performing partial removal process S30 before the adhesive force with respect to the to-be-adhered body of the adhesive sheet stuck to the to-be-adhered body in pasting process S10 exceeds 2N / 25mm. The laminated body 1 firmly joined to the complex 10 can be manufactured, and the above-mentioned problem can be avoided or alleviated in some removal process S20.

In some aspects, the adhesive force A _P with respect to the to-be-adhered body of the adhesive sheet at the time of a some removal process may be less than 2N / 25mm, for example from a viewpoint of the peelability of a 2nd area | region, for example, 1.5N / 25mm Less than, 1.3 N / 25 mm or less, 1 N / 25 mm or less, or 0.8 N / 25 mm or less. A lower limit of the adhesive strength of _P is not particularly limited, from the viewpoint of suppressing the displacement or lifting of the first area of the cut step and the portion removing step, for example, it may be a 0.005N / 25mm or more, may be 0.01N / 25mm or more 0.05 N / 25 mm or more may be sufficient, 0.1 N / 25 mm or more may be sufficient, and 0.2 N / 25 mm or more may be sufficient.

The manufacturing method disclosed here can be performed preferably using the adhesive sheet whose adhesive force (Hereinafter, it is also called adhesive force after 24 hours of room temperature) is 2 N / 25mm or less after 24 hours progress at 23 degreeC, after bonding to a polyimide. . According to such an adhesive sheet, it can respond flexibly to the lead time of the manufacturing process of a laminated body. The upper limit of the adhesive strength after the room temperature for 24 hours, for example, be about the same as either the upper limit of the adhesive strength A _P exemplified above. The lower limit of the adhesive strength after the room temperature for 24 hours, for example, be about the same as either the lower limit of the adhesive strength A _P exemplified above.

After performing some removal process S30, you may further perform adhesive force raising process S40 which raises the adhesive force with respect to the to-be-adhered body 10 of adhesive piece 21A, 21B as needed. According to the manufacturing method including such an adhesive force raising process, the period until the target laminated body (namely, the laminated body whose adhesive force with respect to the to-be-adhered body of an adhesive piece is 5N / 25mm or more) can be shortened. Thereby, productivity of a laminated body can be improved. Moreover, there exists a tendency for the laminated body with higher adhesive force with respect to the to-be-adhered body of an adhesive piece to be manufactured by performing the said adhesive force raising process.

Adhesive force raising process S40 may be a process of providing the stimulus which promotes the raise of the adhesive force of adhesive piece 21A, 21B. The content of the said magnetic pole can be suitably selected according to the type etc. of the adhesive sheet to be used. Examples of the stimulus may include heating, irradiation of actinic rays, presses (pressurization), and the like. These stimuli can be applied individually by 1 type or in combination of 2 or more types.

In addition, in the laminated body manufacturing method disclosed here, an adhesive force raising process is not an essential process, considering the kind of adhesive sheet to be used, productivity and performance of a desired laminated body, manufacturing equipment, manufacturing cost, etc. of the said laminated body, etc. It is an arbitrary process which can be employ | adopted suitably. For example, the adhesive force with respect to the to-be-adhered body of an adhesive sheet exceeds 2 N / 25mm also in the aspect which does not perform a special adhesive force raising process after some removal processes by appropriate selection of the adhesive sheet used for manufacture of a laminated body. A partial removal process may be performed before it, and the laminated body whose adhesive force with respect to the said to-be-adhered body of this adhesive sheet is 5 N / 25 mm or more can be manufactured.

The adhesive piece contained in the laminated body manufactured by the method disclosed here contains a base material layer and an adhesive layer, and is bonded to the to-be-adhered body through the said adhesive layer. Thus, in the laminated body obtained, that the adhesive piece and the to-be-adhered body are joined by the adhesive, ie, the adhesive maintains desired viscoelasticity, is the flexibility, impact resistance, and stress of the laminate produced by the method disclosed herein. It is preferable from a viewpoint of loosening property, low temperature characteristic, adhesiveness of an adherend and an adhesive piece, etc.

In addition, in the example shown in FIG. 2, although the to-be-adhered body 10 and the adhesive sheet 20 of substantially the same size are affixed so that the whole surface (whole area | region) of the one side of the to-be-adhered body 10 may be stuck, the to-be-adhered body ( The sticking aspect of the adhesive sheet with respect to 10) is not limited to this. For example, you may stick so that an adhesive sheet may cover only one partial area | region of the to-be-adhered body, and may stick so that a part of adhesive sheet may protrude from an adherend. In addition, in the adhesive sheet used for sticking process S10, the 1st area | region and 2nd area should just be connected so that these areas can be handled as a series of sheet | seat, In that, the 1st area | region and agent It is not disturbed that cutting auxiliary structures, such as a cutting line (cutting line etc.) and a half cut, are provided in the boundary of two areas. Here, half cut means the incision of the depth which does not penetrate an adhesive sheet in a thickness direction, and is typically formed as the incision of the depth which does not penetrate a base material layer in a thickness direction. Such cutting can be formed by, for example, entering the processing blade from the back surface of the substrate layer (the side opposite to the side on which the adhesive layer is laminated) to a depth not penetrating the substrate layer. In one embodiment, from the viewpoint of improving the handleability of the pressure sensitive adhesive sheet, reducing the manufacturing cost, and the like, an adhesive sheet having no cutting auxiliary structure provided at the boundary between the first region and the second region can be preferably used. In addition, the adhesive sheet used for sticking process S10 may be provided with the indication which helps for the position alignment of the said adhesive sheet and a to-be-adhered body. The display may be a structural display such as a through hole, a cutout, a recess, or the like, or may be a visual display by an optically detectable marking (for example, printing or coloring), or an arrangement (for example, identification) of another member. Label attachment, fixing of elements that enable signal transmission or reflection). Such a display may be provided in one or both of the first region and the second region, or may be provided at the boundary between the first region and the second region.

In addition, in the example shown in FIG. 4, in cut process S20, although the linear cutting process continued to the depth which penetrates an adhesive sheet and reaches the to-be-adhered body surface, the aspect of a cutting process is not limited to this. For example, as long as some removal process S30 can be performed suitably, the 1st area | region and 2nd area | region after cut process S20 may be partially connected. As an example of such a cutting process, the cutting process in which a cutting line etc. are discontinuous, the half cut processing, the process which combined the cutting line and the half cut (for example, the cut part which penetrates a base material layer, and the depth not penetrating the said base material layer) Cutting process of the aspect which repeats this alternately), etc. are mentioned. In addition, the said cutting process may be performed in the depth which penetrates an adhesive sheet, and reaches a to-be-adhered body surface, may be performed to penetrate an adhesive sheet further, and may reach to a partial depth from the surface of a to-be-adhered body, and does not penetrate an adhesive sheet It may be performed at a depth (that is, half cut). In the manufacturing method disclosed here, since the adhesive force with respect to the to-be-adhered body of the adhesive sheet is suppressed low at the time of performing some removal process S30, so that a 1st area | region and a 2nd area may be completely separated at least to the depth which penetrates a base material layer. It is preferable to perform a cutting process. This can be advantageous from the viewpoints of improvement in pick-up property of the second region in some removal step S30, prevention of lifting or misalignment of the first region, improvement in appearance accuracy of the first region, and the like.

In the example shown in FIG. 4, the one end and the other end of the 2nd area | region extended linearly reach the end of an adhesive sheet. Thus, setting the said 2nd area so that at least one end of a 2nd area may reach the end of an adhesive sheet is preferable from the viewpoint of the pick-up property of the 2nd area in some removal process S30. In an aspect in which the second region does not reach the end of the pressure sensitive adhesive sheet, the second region can be picked up by, for example, attaching and pulling up a strongly adhesive adhesive tape on the back of the second region at one end of the second region. Can be. Such a pick-up method can also be employed in an embodiment in which at least one end of the second region reaches the end of the adhesive sheet. The laminated body manufacturing method disclosed here WHEREIN: The adhesive force with respect to the said to-be-adhered body of the adhesive sheet at the time of a some removal process is 2 N / 25mm or less, The 2nd by the method of sticking and pulling up an adhesive tape as mentioned above. It is advantageous from the viewpoint of improving pickup performance of the region.

In the aspect in which the second region is set to reach the end of the pressure sensitive adhesive sheet, the width at which the second region reaches the end of the pressure sensitive adhesive sheet is preferably 0.2 mm or more from the viewpoint of pickup properties, and is 0.5 mm or more. 1 mm or more may be sufficient as it. In order to raise pick-up property, you may comprise so that the width | variety of the said 2nd area | region may become wide in the vicinity which reach | attains the 2nd area | region to the edge of an adhesive sheet. In addition, it is preferable that the width | variety which the said 2nd area | region reaches the end of the said adhesive sheet from the viewpoint of miniaturization of the product (electronic device etc.) containing the laminated body obtained by the manufacturing method disclosed here is 10 mm or less, It is more preferable to set it as 8 mm or less.

When the laminated body manufacturing method disclosed here includes an adhesive force raising process, the grade which raises adhesive force in the said process is not specifically limited, Compared with the adhesive force before the said process, the lamination obtained through the adhesive force after this process or the said process. The adhesive force of the sieve should just be relatively high. In some aspects, the adhesive force raising process has a relationship between adhesive force A ₀ [N / 25mm] to the adherend before the step and adhesive force A ₁ [N / 25mm] to the adherend after the step, Preferably, the ratio A ₁ / A ₀ is satisfied. That is, in an adhesive force raising process, it is preferable to raise the adhesive force with respect to the to-be-adhered body of an adhesive sheet to 2 times or more before the said process. According to such an adhesive force raising process, there exists a tendency for the ease of removal of a 2nd area | region in a partial removal process, and the strong adhesiveness with respect to the to-be-adhered body of the adhesive piece in the manufactured laminated body to be compatible suitably. In some embodiments, 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 ratio (A ₁ / A ₀ ) is not particularly limited, but is preferably 10000 or less, 5000 or less, or 2000 or less from the viewpoint of suppressing positional shift and lifting of the first region before the adhesive force raising step. . According to JIS Z0237, each of the adhesive strengths A ₀ and A ₁ is a peel strength from the adherend of the adhesive sheet under conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min in an environment of 23 ° C. and 50% RH. It can grasp by measuring.

The adhesive force A ₀ with respect to the to-be-adhered body of the adhesive sheet before an adhesive force raising process may be about the same as adhesive force A _P at the time of the said partial removal process, for example. Therefore, each upper limit and each lower limit of the adhesive force A _P illustrated above can be applied to each of the upper limit value and the lower limit value which the adhesive force A ₀ can independently take. Furthermore, each upper limit value and a lower limit value of the adhesive force A _P exemplified above are, each independently, can be applied to each can, the initial adhesive strength B _0, which will be described later to take the upper limit value and the lower limit value.

In the laminate produced by the method disclosed herein, the adhesive force A _F with respect to the adherend of the adhesive piece may be, for example, more than 5 N / 25 mm, 7 N / 25 mm or more, 10 N / 25 mm or more, or 12 N. / 25mm or more may be sufficient. It is preferable that adhesive force A _F is high from a viewpoint of suppressing peeling and lifting from the to-be-adhered body of the adhesive piece at the time of use of the said laminated body. The upper limit of the adhesive force A _F is not particularly limited. In some aspects, the adhesive force A _F may be, for example, 50 N / 25 mm or less, 40 N / 25 mm or less, from the viewpoint of facilitating compatibility with easy peeling of the second region in the partial removal step. 35 N / 25 mm or less may be sufficient, and 30 N / 25 mm or less may be sufficient.

Further, in the embodiment, including adhesive force increase process, the adhesive strength A ₁ [N / 25mm] onto an adherend of the adhesive sheet in after the adhesive force increases step is, for example, pressure-sensitive adhesive convenience adherend in the produced layered product It may be about the same as adhesive force A _{F to} . Therefore, each upper limit and each lower limit of the adhesive force A _F illustrated above can be applied to each of the upper limit value and the lower limit value which the adhesive force A ₁ can independently take. In addition, each upper limit and the lower limit of the adhesive force A _F illustrated above can be applied also to each of the upper limit and the lower limit which the adhesive force B ₁ after stimulation mentioned below can respectively independently take.

The content of the stimulus applied to the adhesive sheet in the adhesive force raising step is, for example, the adhesive force increase ratio (B ₁ / defined as the ratio to the adhesive force B ₁ after stimulation of the initial adhesive force B ₀ to the polyimide of the adhesive sheet to be used. B ₀ ) may be set to satisfy a predetermined target value. Initial adhesive force B ₀ and post-stimulation adhesive force B ₁ are measured by the method as described in the Example mentioned later.

When the manufacturing method disclosed herein include adhesion rising step, the adhesive force increases step, the adhesion increase ratio (B ₁ / B ₀₎ is for example preferably performed such that at least 2, and the adhesive force increase ratio (B ₁ / B ₀ ) is more preferably 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 and improving the productivity of the laminate, the adhesive force raising step may be performed so that the adhesive force increase ratio (B ₁ / B ₀ ) is approximately 10000 or less, 5000 or less, or 2000 or less. Can be. In some embodiments, the adhesive force increase ratio is (B ₁ / B ₀₎ is, for example, even 1000 or less, 500 or less is even, and even less than 200, 100 is even less.

In addition, in a flexible display panel, a flexible printed wiring board (FPC), a device in which the display panel and the wiring board are integrated, a flexible substrate material is used, and a polyimide film is used as the substrate material in view of heat resistance and dimensional stability. There are many. The aforementioned adhesive strength with respect to the polyimide B _0, B _1, or the adhesive strength rises ratio (B ₁ / B _0), which represents the pressure-sensitive adhesive sheet is, in aspects of the polyimide body deposition used in the manufacture of the layered product, in the part removal process of claim Peeling workability | operativity of 2 area | regions is good, and when using the obtained laminated body, it can exhibit the property that it is excellent in adhesive reliability with a to-be-adhered body. Using this property, the film coverlay of the FPC can be formed with high precision and efficiently. Thus, the method disclosed herein can be preferably applied, for example, to the production of FPC with a film coverlay.

The heating temperature in the case of heating as a stimulus imparted to the pressure-sensitive adhesive sheet in the pressure-sensitive adhesive raising step is not particularly limited, and considering workability, economical efficiency, heat resistance of the substrate layer and adherend to be included in the pressure-sensitive adhesive sheet, etc. Can be set. The heating temperature may be, for example, less than 150 ° C, 120 ° C or less, 100 ° C or less, 80 ° C or less, or 70 ° C or less. In addition, the said heating temperature can be 40 degreeC or more, 50 degreeC or more, or 60 degreeC or more, for example, you may be 80 degreeC or more, and you may be 100 degreeC or more. According to higher heating temperature, adhesive force can be raised by a shorter process. Heating time is not specifically limited, For example, it may be 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less. Alternatively, the heat treatment may be performed for a longer period of time (eg, 2 hours or more, 5 hours or more) as long as no significant thermal degradation occurs in the pressure sensitive adhesive sheet or the adherend. In addition, heat processing may be performed at once, and may be divided and performed in multiple times.

The adhesive sheet used for a sticking process may contain only one area | region (1st area | region) used as the adhesive piece which comprises a laminated body in one adhesive sheet, for example, spaced apart from each other as shown in FIG. Two first regions may be included, or three or more first regions may be included. When one adhesive sheet contains a some 1st area | region, the shape of those 1st area | regions may be same or different. Similarly, the adhesive sheet used for a sticking process may contain only one 2nd area | region which peels and removes in one part removal process in one adhesive sheet, for example as shown in FIG. Alternatively, three or more may be included. When one adhesive sheet contains a some 2nd area | region, the shape of those 2nd area may be same or different.

In the laminated body manufacturing method which concerns on some aspects, as an adhesive sheet and a to-be-adhered body used for a sticking process, what contains two or more units corresponding to the laminated body manufactured by this method can be used. This aspect is a process performed after the said sticking process, and can further include the division process which divides the said adhesive sheet and the to-be-adhered body into the said unit. The said division process can be performed at arbitrary times, after performing a sticking process. For example, by performing a division process at least after finishing the cut process, a plurality of units can be integrated to perform the cut process. The manufacturing method disclosed here can be performed by the aspect which includes the said division process between the (a) cut process and a partial removal process, for example. In the manufacturing method including an adhesive force raising process after a partial removal process, you may implement the said division process in the aspect included, for example between (b) partial removal process and adhesive force raising process, or (c) after an adhesive force raising process. You may combine 1 or 2 or more of the aspect of said (a)-(c). In addition, the said aspect (a) can be preferably implemented using the adhesive sheet provided with the adhesive layer 2 mentioned later, for example. The said aspect (b) and the said aspect (c) can be implemented preferably using the adhesive sheet provided with the adhesive layer 1 or the adhesive layer 2 mentioned later, for example.

<< manufacturing apparatus >>

As for the laminated body manufacturing method disclosed here, for example, as shown in FIG. 5, the sticking mechanism 51 which affixes the adhesive sheet 20 to the to-be-adhered body 10, and the 1st of the adhesive sheet 20 are shown. The cut mechanism 52 which performs cutting at the boundary between the region 21 and the second region 22 and the second region 22 while leaving the first region 21 on the adherend 10 are avoided. It can implement using the laminated body manufacturing apparatus 50 provided with the peeling mechanism 53 which peels and removes from the complex 10. FIG.

The sticking mechanism 51 is comprised so that the sticking process in any manufacturing method disclosed here can be performed, for example, a to-be-adhered body supply means, an adhesive sheet supply means, the crimping means to the to-be-adhered body, etc. It may include one or two or more of. The cut mechanism 52 is comprised so that the cut process in any manufacturing method disclosed here can be implemented, and can contain 1 or 2 or more of cutting means as illustrated above. The peeling mechanism 53 is comprised so that partial removal process in either method disclosed here can be performed, for example, 1 or 2 or more, such as a pickup means, a holding means, a peeling means, etc. of a 2nd area | region. It may include.

Moreover, the laminated body manufacturing apparatus which can be used for implementation of the laminated body manufacturing method of an aspect containing an adhesive force raising process is a mechanism which gives the stimulus which raises the adhesive force with respect to a 1st area | region, for example, adhesive force not shown in figure. It may further include a lift mechanism. An adhesive force raising mechanism is comprised so that the adhesive force raising process in any method disclosed here can be performed by providing the magnetic pole which can raise the adhesive force of the said adhesive sheet with respect to an adhesive sheet. The adhesive force raising mechanism may include, for example, one or two or more of UV irradiation means (UV irradiation lamps, light path adjustment mirrors, etc.), heating means (hot air heaters, infrared heaters, electric heaters, and the like), press means, and the like.

Moreover, the manufacturing apparatus used for the laminated body manufacturing method of the aspect containing a division process can further include the division mechanism not shown. The said division mechanism can be comprised so that a division process can be performed using well-known division means, such as a cutting | disconnection by a thomson blade, a pinnacle blade, a rotary blade, a knife, etc., or laser cutting, waterjet cutting, blade cutting.

<< adhesion sheet >>

Hereinafter, although the some example of the adhesive sheet which can be employ | adopted preferably for implementing the laminated body manufacturing method disclosed here is demonstrated, it is not intending to limit the scope of the present invention.

The laminated body manufacturing method disclosed here can be performed preferably using the adhesive sheet of the structure containing a base material layer and the adhesive layer laminated | stacked at least on the to-be-adhered body side of this base material layer. According to the adhesive sheet of the structure by which the adhesive layer was laminated | stacked on the base material layer, since an adhesive layer can be reinforced by the said base material layer, it is easy to peel a 2nd area | region from a to-be-adhered body in some removal processes.

<Base layer>

As said base material layer, various film base materials can be used preferably. The film substrate may be a porous substrate, such as a foam film or a nonwoven fabric sheet, may be a nonporous substrate, or may be a substrate having a structure in which a porous layer and a nonporous layer are laminated. In some aspects, as said film base material, what contains the resin film which can be independently shape-retained (independent or independent) as a base film can be used preferably. The "resin film" here means a nonporous structure, and typically means a resin film (voidless) that contains substantially no bubbles. Therefore, the said resin film is a concept distinguished from a foam film or a nonwoven fabric. The resin film may have a single layer structure or a multilayer structure of two or more layers (for example, a three layer structure).

As a resin material which comprises a resin film, For example, polyamide (PA), polyimide (PI), polyamideimide (PAI), polyether, such as polyester, a polyolefin, nylon 6, nylon 66, a partially aromatic polyamide, etc. Ether ketone (PEEK), polyether sulfone (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene Fluorine resins, such as (PTFE), acrylic resin, polyacrylate, polystyrene, polyvinyl chloride, resin, such as polyvinylidene chloride, can be used.

The said resin film may be formed using the resin material containing 1 type of such resin independently, and may be formed using the resin material which blended 2 or more types. Non-stretching may be sufficient as the said resin film, and what was extended | stretched (for example, uniaxial stretching or biaxial stretching) may be sufficient as it. For example, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, non-stretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene Resin films, such as a (LLDPE) film and a PP / PE blend film, can be used preferably. PET film, PEN film, PPS film, and PEEK film are mentioned as an example of the resin film from which a strength and dimensional stability are preferable from a viewpoint. PET film and PPS film are especially preferable from a viewpoint of availability, etc., PET film is especially preferable.

In the resin film, known additives such as light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, and anti blocking agents are required within a range that does not significantly impair the effects of the present invention. It can mix | blend accordingly.

The manufacturing method of a resin film is not specifically limited. For example, conventionally well-known general resin film molding methods, such as extrusion molding, inflation molding, T diecast molding, and calender roll molding, can be employ | adopted suitably.

The base layer may be substantially configured from such a base film. Alternatively, the base material layer may include an auxiliary layer in addition to the base film. As an example of the said auxiliary layer, surface treatment layers, such as an optical property adjustment layer (for example, a coloring layer, an antireflection layer), a printing layer, a laminate layer, an antistatic layer, an undercoat layer, a peeling layer, etc., for giving a desired appearance to a base material layer Can be mentioned.

On the surface of the base material layer on which the pressure-sensitive adhesive layer is laminated, as necessary, such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, formation of a undercoat layer by application of a primer (primer), The surface treatment conventionally known may be performed. Such surface treatment may be a process for improving the anchoring property to the base material layer of an adhesive layer. The composition of the primer used for formation of an undercoat layer is not specifically limited, It can select from a well-known thing suitably. Although the thickness of the undercoat layer is not particularly limited, usually about 0.01 μm to 1 μm is suitable, and about 0.1 μm to 1 μm is preferable. As another process which can be performed to a base material layer as needed, an antistatic layer formation process, a colored layer formation process, a printing process, etc. are mentioned. These treatments can be applied alone or in combination.

<< adhesive layer >>

The composition of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited. The pressure sensitive adhesive exhibits rubber elasticity at room temperature, such as acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluorine polymers, which are known in the field of pressure sensitive adhesives. One or two or more kinds of various polymers may be included as the base polymer (the main component in the polymer component, that is, the component occupying more than 50% by weight). Especially, as a preferable adhesive, an acrylic adhesive and a rubber adhesive are illustrated. Here, an acrylic adhesive means the adhesive which contains an acrylic polymer as a base polymer. The same applies to the rubber pressure sensitive adhesive. In addition, the said acryl-type polymer means the polymer whose 50 weight% or more of the monomer components whole quantity which comprises this acryl-type polymer is an acryl-type monomer. In addition, in this specification, an acryl-type monomer means the monomer which has at least 1 (meth) acryloyl group in 1 molecule. In addition, the said (meth) acryloyl group is the meaning which points out acryloyl group and methacryloyl group comprehensively.

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

<Adhesive layer containing base polymer A and siloxane structure containing polymer B>

The pressure-sensitive adhesive layer 1 contains the base polymer A and the siloxane structure-containing polymer B, and after being bonded to the adherend, the adhesive force is suppressed low for a while in the room temperature region (for example, 20 ° C to 30 ° C), Aging (which may be heating, time-lapse, a combination thereof, etc.) may exhibit a property of greatly increasing the adhesive force. Therefore, it can be used suitably for the laminated body manufacturing method disclosed here. The pressure-sensitive adhesive layer 1 may be formed of a pressure-sensitive adhesive composition containing a base polymer A or a precursor thereof and a siloxane structure-containing polymer B. The form of the pressure-sensitive adhesive composition is not particularly limited, and may be, for example, various forms such as a water dispersion type, a solvent type, a hot melt type, and an active light curing type (for example, UV curing type).

(Base polymer A)

As base polymer A (Hereinafter, it may abbreviate as "polymer A") of the adhesive layer 1, an acryl-type polymer can be used preferably. When an acryl-type polymer is used as the polymer A, there exists a tendency for favorable compatibility with the polymer B to be easy to be obtained. The good compatibility between the polymer A and the polymer B is an adhesive having a low adhesiveness in some removal steps and a strong adhesiveness after an adhesive force increase treatment (for example, a heat treatment) by improving the mobility of the polymer B in the adhesive layer. It is preferable because it can contribute to the realization of the layer (1). It is preferable that 50 weight% or more of the adhesive layer 1 is an acrylic polymer.

As an acryl-type polymer, 40 weight% or more of the monomer components whole quantity which comprises the said acryl-type polymer can use preferably (meth) acrylic-acid alkylester, for example. (Meth) acrylic acid alkyl ester, it may preferably be used having an alkyl group of a straight-chain or branched one having 1 to 20 carbon atoms (i.e., the C _1-20) ester end. In the point which is easy to balance a characteristic, the ratio of the (meth) acrylic-acid C _1-20 alkylester in the constituent monomer component whole quantity of an acrylic polymer may be 50 weight% or more, 55 weight% or more, for example, 60 weight % Or more may be sufficient. For the same reason, the ratio of the (meth) acrylic acid C _1-20 alkyl ester in the total amount of the constituent monomer components may be, for example, 99.9 wt% or less, 98 wt% or less, or 95 wt% or less. In some aspects, the ratio of (meth) acrylic-acid _C1-20 alkylester in monomer component whole quantity may be 90 weight% or less, 85 weight% or less, or 80 weight% or less, for example.

Non-limiting examples of (meth) acrylic acid C _1-20 alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, ( Heptyl methacrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl acrylate, isonyl acrylate, (meth) isonyl acrylate, (meth) decyl acrylate, (meth) Isodecyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isotridodecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, (meth Hexadecyl acrylate, heptadecyl (meth) acrylate, (meth) arc Acid, stearyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl.

Among these, it is preferable to use at least (meth) acrylic acid C _1-18 alkyl ester, and it is more preferable to use at least (meth) acrylic acid C _1-14 alkyl ester. In some embodiments, the constituent monomer component of the acrylic polymer is selected from (meth) acrylic acid C _4-12 alkyl esters (preferably acrylic acid C _4-10 alkyl esters, for example acrylic acid C _6-10 alkyl esters). It may include at least one. For example, an acrylic polymer containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) is preferable, and an acrylic polymer containing at least 2EHA is particularly preferable. Examples of other (meth) acrylic acid C _1-18 alkyl esters that may be preferably used include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA). ) And isostearyl acrylate (ISTA).

The structural monomer component of an acryl-type polymer may contain the other monomer (copolymerizable monomer) copolymerizable with the (meth) acrylic-acid alkylester as needed with the (meth) acrylic-acid alkylester as a main component. As a copolymerizable monomer, the monomer which has a polar group (for example, a carboxy group, a hydroxyl group, etc.) can be used suitably. The monomer having a polar group may be helpful for introducing a crosslinking point into the acrylic polymer or for increasing the cohesive force of the acrylic polymer. A copolymerizable monomer can be used individually by 1 type or in combination of 2 or more types.

As a nonlimiting specific example of a copolymerizable monomer, the following are mentioned.

Carboxyl group-containing monomers: For example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.

Hydroxy group-containing monomers: for example, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-hydroxybutyl, (meth 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl ( (Meth) acrylic acid hydroxyalkyl such as meth) acrylate; Monomers having a hydroxy group and an amide group, such as N- (2-hydroxyethyl) acrylamide (HEAA).

Nitrogen containing monomers: for example, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole , Vinyl morpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholindione , N-acryloyl morpholine, N-vinylcarboxylic acid amides, and the like.

In addition, a cyano group containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, an epoxy group containing monomer, a vinyl ether monomer, a sulfo group containing monomer, a phosphoric acid group containing monomer, an acid anhydride group containing monomer, etc.

When using such a copolymerizable monomer, the usage-amount is not specifically limited, Usually, it is suitable to set it as 0.01 weight% or more of the monomer component whole quantity. From the viewpoint of better exerting the effect of the use of the copolymerizable monomer, the amount of the copolymerizable monomer may be 0.1% by weight or more, or 1% by weight or more of the total amount of the monomer components. In addition, the usage-amount of a copolymerizable monomer can be 50 weight% or less of monomer component whole quantity, and it is preferable to set it as 40 weight% or less. Thereby, the cohesion force of an adhesive can be prevented from becoming high too much, and the tactile feeling in normal temperature (25 degreeC) can be improved.

In some aspects, it is preferable that an acryl-type polymer contains at least 1 sort (s) of monomer chosen from the group which consists of an N-vinyl cyclic amide and a hydroxyl-containing monomer as the structural monomer component.

By using N-vinyl cyclic amide, the cohesion force and polarity of an adhesive can be adjusted, and the adhesive force after heating as an stimulus which raises adhesive force (henceforth "adhesive force after heating") can be improved. As a specific example of N-vinyl cyclic amide, the thing which has a corresponding structure among the nitrogen containing monomer mentioned above is mentioned. Particularly preferred examples include N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam. Although the usage-amount of N-vinyl cyclic amide is not specifically limited, Usually, it is suitable to set it as 0.01 weight% or more (preferably 0.1 weight% or more, for example 0.5 weight% or more) of the whole quantity of the constituent monomer components of an acryl-type polymer. . In some aspects, the usage-amount of N-vinyl cyclic amide may be 1 weight% or more of the said monomer component whole quantity, may be 5 weight% or more, may be 8 weight% or more, and 10 weight% or more You may be 12 weight% or more. In addition, from the viewpoint of improving the feeling of tack at normal temperature (25 ° C.) and improving the flexibility at low temperature, the amount of N-vinyl cyclic amide is usually preferably 40% by weight or less of the total amount of the monomer component, and 30% by weight. It may be% or less, may be 25 parts by weight or less, 20% by weight or less, or 18% by weight or less.

By using a hydroxyl-containing monomer, the cohesion force and polarity of an adhesive can be adjusted, and the adhesive force after heating can be improved. In addition, a hydroxyl-containing monomer provides the reaction point with the crosslinking agent (for example, isocyanate type crosslinking agent) mentioned later, and can raise the cohesion force of an adhesive by a crosslinking reaction. Suitable examples of the hydroxyl group-containing monomers include 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4HBA), and N- (2-hydroxyethyl) acrylamide (HEAA). Although the usage-amount of a hydroxyl-containing monomer is not specifically limited, Usually, it is suitable to set it as 0.01 weight% or more (preferably 0.1 weight% or more, for example 0.5 weight% or more) of the whole amount of the constituent monomer components of an acrylic polymer. In some aspects, the usage-amount of a hydroxyl-containing monomer may be 1 weight% or more of the said monomer component whole quantity, may be 5 weight% or more, and may be 10 weight% or more. In addition, from the viewpoint of improving the feeling of tack at room temperature (25 ° C.) and improving the flexibility at low temperatures, the amount of the hydroxyl group-containing monomer is usually appropriately set to 40% by weight or less of the total amount of the monomer components, and 30% by weight or less. It may be sufficient as it, you may be 20 weight% or less, and you may be 10 weight% or less or 5 weight% or less.

In some aspects, N-vinyl cyclic amide and a hydroxyl-containing monomer can be used together as a copolymerizable monomer. In this case, the total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer may be, for example, 0.1% by weight or more, 1% by weight or more, 5% by weight or more, or 10% by weight of the entire amount of the constituent monomer components of the acrylic polymer. % Or more, 15 weight% or more, 20 weight% or more, or 25 weight% or more may be sufficient. The total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer can be, for example, 50% by weight or less of the monomer component whole amount, and preferably 40% by weight or less.

In the aspect which uses N-vinyl cyclic amide and a hydroxyl group containing monomer together, the relationship (weight basis) of the usage-amount ( _WN ) of N-vinyl cyclic amide and the usage-amount ( _WOH ) of a hydroxyl-containing monomer is not specifically limited. W _N / W is _OH, for example, may be a less than 0.01, usually be either a proper and, at least 0.1 less than 0.05, and even 0.2 or more, and even 0.5 or more, and may be 0.7 or more. In addition, W _N / W _OH is, for example, is 100 even less, usually 20 is less than the even suitable, and 10 or less, and even 5 or less, and even, more than 2, less than 1.5 and even 1.3 is less even.

Tg of polymer A is typically less than 0 degreeC, Preferably it is less than -10 degreeC, More preferably, it is less than -20 degreeC. The adhesive containing the 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), so that the adhesive force is easily increased by performing heat treatment at any timing. . In some embodiments, 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 viewpoint of the availability of materials and the improvement of the cohesive force of the pressure-sensitive adhesive layer, usually, Polymer A having a Tg of -80 ° C or higher can be suitably employed.

In this specification, Tg of a polymer means Tg calculated | required by the formula of Fox based on the nominal value described in a literature, a catalog, etc., or the composition of the monomer component used for preparation of the said polymer. The formula of Fox is a relationship between the Tg of a copolymer and the glass transition temperature Tgi of the homopolymer which homopolymerized each of the monomers which comprise this copolymer as described below.

1 / Tg = Σ (Wi / Tgi)

In the formula of Fox, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction of the monomer i in the copolymer (copolymer ratio on a weight basis), and Tgi is the homopolymer of the monomer i. The glass transition temperature (unit: K) is shown. When the polymer of interest concerning the specification of Tg is a homopolymer, the Tg of the homopolymer and the polymer Tg of the object coincide.

As a glass transition temperature of the homopolymer used for calculation of Tg, the value described in well-known data shall be used. Specifically, numerical values are exemplified in the "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989). The highest value is employ | adopted about the monomer in which several types of values are described in the said polymer handbook.

Although it does not specifically limit, It is suitable that the weight average molecular weight (Mw) of the polymer A is usually about 50,000 or more normally, For example, 100,000 or more may be sufficient from a viewpoint of obtaining the adhesive which shows a more favorable cohesion, 200,000 or more 300,000 or more may be sufficient, 500,000 or more may be sufficient, and 700,000 or more may be sufficient as it. Moreover, it is suitable that Mw of the polymer A is about 5 million or less normally. Such a polymer A of Mw is easy to form the adhesive which shows moderate fluidity (mobility of a polymer chain), and is suitable for realizing the adhesive sheet with a high adhesive force rise ratio. In some aspects, Mw of the polymer A may be 3 million or less, 2 million or less, or 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 method and conditions described in the Example mentioned later.

The method of obtaining an acrylic polymer is not specifically limited, Various polymerization methods known as a synthesis method of an acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, suspension polymerization method, and a photopolymerization method, can be employ | adopted suitably.

The initiator used for superposition | polymerization can be suitably selected from a conventionally well-known thermal initiator, a photoinitiator, etc. according to the polymerization method. Non-limiting examples of thermal initiators include azo initiators such as 2,2'-azobisisobutyronitrile (AIBN), persulfates such as potassium persulfate, peroxide initiators, and redox initiators. Non-limiting examples of the photoinitiator include benzoin ether photoinitiator, acetophenone photoinitiator, α-ketol photoinitiator, aromatic sulfonyl chloride photoinitiator, photoactive oxime photoinitiator, benzoin photoinitiator, benzyl photoinitiator An initiator, a benzophenone type photoinitiator, a ketal type photoinitiator, a thioxanthone type photoinitiator, an acylphosphine oxide type photoinitiator, etc. are mentioned. An initiator can be used individually by 1 type or in combination of 2 or more type.

In some aspects, the solution polymerization method can be preferably used as a method of obtaining an acrylic polymer. As a solvent of solution polymerization, ethyl acetate, toluene, etc. are used. The solution concentration is usually about 20 to 80% by weight. As an initiator, various well-known things, such as an azo system and a peroxide type, can be used. In order to adjust molecular weight, the chain transfer agent may be used. The reaction temperature is usually about 50 to 80 ℃, the reaction time may be usually about 1 to 8 hours.

In some embodiments, the acrylic polymer is in the form of a partial polymer (acrylic polymer syrup) in which a part of the monomer component is polymerized by irradiating ultraviolet (UV) to a mixture containing an initiator in the monomer component as described above. It may be included in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer. The pressure-sensitive adhesive composition containing such an acrylic polymer syrup can be applied to a predetermined coated object, and UV can be irradiated to complete the polymerization. That is, the acrylic polymer syrup may be regarded as a precursor of the acrylic polymer. The adhesive layer 1 can be formed using the adhesive composition containing these acrylic polymer syrups and the polymer B, for example.

(Siloxane structure containing polymer B)

The siloxane structure-containing polymer B (hereinafter sometimes abbreviated as "polymer B") is a copolymer of a monomer having a polyorganosiloxane skeleton (hereinafter also referred to as "monomer S1") and a (meth) acrylic monomer. The polymer B can function as an adhesive force increase retardant which contributes to the suppression of initial stage adhesive force and the improvement of adhesive force rise ratio by the low polarity and motility of the polyorganosiloxane structure derived from monomer S1. The monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used. The monomer S1 promotes the localization of the polymer B to the pressure-sensitive adhesive layer surface in the pressure-sensitive adhesive sheet before use (before adhesion to the adherend) due to the low polarity derived from the structure, and the light peelability at the initial stage of bonding (low adhesion) ). As monomer S1, the thing of the structure which has a polymerizable reactor at one end can be used preferably. By copolymerization of such a monomer S1 and a (meth) acrylic-type monomer, the polymer B which has a polyorganosiloxane skeleton in a side chain is formed. The polymer B having such a structure tends to have a low initial adhesive force and a high adhesive force increase ratio due to the mobility and mobility of the side chains.

As monomer S1, the compound represented by following General formula (1) or (2) can be used, for example. More specifically, X-22-174ASX, X-22-2426, X-22-2475, KF-2012, etc. are mentioned as single-end reactive silicone oil by Shin-Etsu Chemical Co., Ltd. make. Monomer S1 can be used individually by 1 type or in combination of 2 or more type.

Here, in said general formula (1), (2), R <^3> is hydrogen or methyl, R <^4> is a methyl group or monovalent organic group, m and n are integers 0 or more.

It is preferable that the functional group equivalent of monomer S1 is 700 g / mol or more and less than 15000 g / mol, for example, It is more preferable that it is 800 g / mol or more and less than 10000 g / mol, It is more preferable that it is 850 g / mol or more and less than 6000 g / mol, 1500 g / mol It is especially preferable that it is mol or more and less than 5000 g / mol. If the functional group equivalent of monomer S1 is less than 700 g / mol, initial stage adhesive force may not be fully suppressed. If the functional group equivalent of monomer S1 is 15000 g / mol or more, the raise of adhesive force may become inadequate. If the functional group equivalent of monomer S1 is in the said range, it will be easy to adjust compatibility (for example, compatibility with polymer A) and mobility in an adhesive layer to an appropriate range, and the initial low adhesiveness and the steel at the time of using a laminated body It becomes easy to implement the adhesive sheet which makes adhesiveness compatible with a high level.

Here, "functional group equivalent" means the weight of the main skeleton (for example, polydimethylsiloxane) couple | bonded with per functional group. About the description unit g / mol, it is converted into 1 mol of functional groups. The functional group equivalent of monomer S1 can be computed from the spectral intensity of ¹ H-NMR (proton NMR) based, for example on nuclear magnetic resonance (NMR). Calculation of the functional group equivalent (g / mol) of monomer S1 based on the spectral intensity of ¹ H-NMR is based on the general structural analysis method which affects ¹ H-NMR spectrum analysis, Unexamined-Japanese-Patent No. 5951153 if necessary. It can carry out with reference to description of.

In addition, when using two or more types of monomers which differ in functional group equivalent as monomer S1, an arithmetic mean value can be used as functional group equivalent of monomer S1. That is, the functional group equivalent weight of the monomer S1 made of a monomer equivalent of the functional group of the other n-type (S1 monomer _1, monomer ₂ S1 ... S1 _n monomer), can be calculated by the following equation.

Functional group equivalent weight of the monomer S1 of the functional group equivalent weight (g / mol) = (monomer S1 ₁ of the functional group equivalent weight × monomer S1 ₁ the amount + monomer S1 ₂ of the functional group equivalent weight × monomer S1 ₂ amount + a ... + monomer S1 _n × monomer S1 _n Compounding amount of) / (mixing amount of monomer S1 ₁ + compounding amount of monomer S1 ₂ + amount of monomer S1 _n )

The content of the monomer S1 may be, for example, 5% by weight or more with respect to the total monomer components for preparing the polymer B, and is preferably 10% by weight or more from the viewpoint of better exerting the effect as an adhesive force retardation agent. 15 weight% or more may be sufficient, and 20 weight% or more may be sufficient. In addition, it is suitable to make content of monomer S1 into 60 weight% or less with respect to all the monomer components for manufacturing polymer B from a polymerization reactivity or compatibility viewpoint, and may be 50 weight% or less, and 40 weight% or less It is good also as 30 weight% or less. When content of monomer S1 is less than 5 weight%, initial stage adhesive force may not be fully suppressed. If 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 for preparation of the polymer B contains the (meth) acrylic-type monomer copolymerizable with monomer S1 in addition to monomer S1. By copolymerizing 1 type, or 2 or more types of (meth) acrylic-type monomer and monomer S1, the mobility of the polymer B in an adhesive layer can be adjusted suitably. Copolymerization of the monomer S1 and the (meth) acrylic monomer may also help to improve the compatibility of the polymer B with the polymer A (eg, the acrylic polymer).

As a (meth) acrylic-type monomer, (meth) acrylic-acid alkylester is mentioned, for example. For example, as the (meth) acrylic acid alkyl ester which can be used when the polymer A is an acrylic polymer, one kind or two or more kinds of the monomers exemplified above can be used as the copolymerizing component of the polymer B. In some embodiments, polymer B is a (meth) acrylic acid C _4-12 alkyl ester (preferably (meth) acrylic acid C _4-10 alkyl ester, for example (meth) acrylic acid C _6-10 alkyl ester) At least 1 type of may be contained as a monomer unit. In some other embodiments, Polymer B comprises at least one of methacrylic acid C _1-18 alkyl esters (preferably methacrylic acid C _1-14 alkylesters, for example methacrylic acid C _1-10 alkylesters). One type can be contained as a monomer unit. The monomer unit which comprises polymer B can contain 1 type (s) or 2 or more types chosen from MMA, BMA, and 2EHMA, for example.

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, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, etc. Can be used. In some embodiments, the polymer B can contain at least 1 sort (s) chosen from dicyclopentanyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate as a monomer unit.

The usage-amount of the said (meth) acrylic-acid alkylester and the (meth) acrylic acid ester which has the said alicyclic hydrocarbon group may be 10 weight% or more and 95 weight% or less with respect to the whole monomer component for preparing polymer B, for example, 20 It may be 95 weight% or more in weight% or more, and may be 30 weight% or more and 90 weight% or less, 40 weight% or more and 90 weight% or less, or 50 weight% or more and 85 weight% or less.

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

In some aspects, by including the monomer unit common to the monomer unit contained in the polymer B also in the polymer A, the mobility of the polymer B in an adhesive layer can be improved, and an adhesive force rise ratio can be improved. It is effective that the common monomer unit is a component which occupies 5 weight% or more of all the monomer units which comprise the polymer B, and 10 weight% or more (more preferably 20 weight% or more, for example, 30 weight% or more) It is preferable that it is a component to occupy. For example, 1 weight% or more may be sufficient as the ratio which the said common monomer unit makes up in the whole monomeric unit which comprises polymer A, Preferably it is 3 weight% or more, More preferably, it is 5 weight% or more, 7 weight% The above may be sufficient. When the ratio which the common monomer unit occupies in all the monomer units which comprise the polymer A becomes high, there exists a tendency for the effect of improving compatibility to be exhibited better. In addition, in view of the balance with other characteristics, the proportion of the common monomer units in all the monomer units constituting the polymer A may be 50% by weight or less, 30% by weight or less, or 15% by weight or less. Non-limiting examples of monomers that can be preferably employed as a common monomer unit include MMA, BMA, 2EHMA, methylacrylate (MA), BA, 2EHA, cyclohexyl (meth) acrylate, isobornyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, and the like.

Mw of the polymer B is not particularly limited. 1000 or more may be sufficient as Mw of the polymer B, for example. In several aspects, Mw of the polymer B may be 10000 or more, may be 12000 or more, 15000 or more, 17000 or more, or 20000 or more may be sufficient from the viewpoint of improving adhesiveness synergy by heating. do. In addition, Mw of the polymer B may be 500000 or less, for example, 350000 or less. In the aspect which makes it easy to peel a 2nd area | region from a to-be-adhered body in some removal process, in some aspects, Mw of the polymer B may be 100000 or less, 70000 or less, 50000 or less, for example, Less than 50000 may be sufficient, Less than 40000 may be sufficient, Less than 35000 may be sufficient, 30000 or less may be sufficient, 28000 or less may be sufficient, and 25000 or less may be sufficient. If Mw of the polymer B is in the range of any of the above-mentioned upper limits and lower limits, the compatibility and mobility in the pressure-sensitive adhesive layer can be easily adjusted to an appropriate range, and the low adhesion in some removal steps and the strong adhesion at the time of using the laminate are at high levels. It becomes easy to be compatible.

Polymer B can be produced by, for example, polymerizing the above-mentioned monomers by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization.

Chain transfer agents can be used to adjust the molecular weight of Polymer B. Examples of the chain transfer agent to be used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol and α-thioglycerol; Thioglycolic acid; Methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isoctyl thioglycolate, and thioglycolate decyl Thioglycolic acid esters such as thioglycolic acid dodecyl, thioglycolic acid ester of ethylene glycol, thioglycolic acid ester of neopentyl glycol, and thioglycolic acid ester of pentaerythritol; α-methylstyrene dimer; Etc. can be mentioned.

Although it does not restrict | limit especially as an usage-amount of a chain transfer agent, Usually, it is 0.05 weight part-20 weight part with respect to 100 weight part of monomers, Preferably it is 0.1 weight part-15 weight part, More preferably, you may be 0.2 weight part-10 weight part. It is suitable. Thus, the polymer B of a suitable molecular weight can be obtained by adjusting the usage-amount of a chain transfer agent. A chain transfer agent can be used individually by 1 type or in combination of 2 or more type.

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

An adhesive layer can contain polymers (optional polymer) other than polymer A and the polymer B as needed in the range which does not largely impair the effect obtained by the technique disclosed here. It is preferable that the usage-amount of such arbitrary polymers is 20 weight% or less of the whole polymer component contained in an adhesive layer normally. In some aspects, the usage-amount of the said arbitrary polymer may be 5 weight% or less of the said polymer component, and may be 1 weight% or less. The pressure-sensitive adhesive layer that does not substantially contain polymers other than the polymer A and the polymer B may be sufficient.

(Bridge)

A crosslinking agent can be used for an adhesive layer as needed for the purpose of adjustment of cohesion force. As a crosslinking agent, a crosslinking agent known in the field of an adhesive can be used, For example, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an oxazoline type crosslinking agent, an aziridine type crosslinking agent, a carbodiimide type crosslinking agent, a metal chelate crosslinking agent, etc. are mentioned. have. In particular, an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent are preferable. A crosslinking agent can be used individually by 1 type or in combination of 2 or more type. The technique disclosed herein can be preferably carried out in an embodiment using at least an isocyanate-based crosslinking agent as the crosslinking agent.

As an example of an isocyanate type crosslinking agent, Lower aliphatic polyisocyanate, such as butylene diisocyanate and hexamethylene diisocyanate; Alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate; Trimethylolpropane / tolylene diisocyanate trimer adduct (for example, tosomer "coronate L"), trimethylolpropane / hexamethylene diisocyanate trimer adduct (for example, tosomer "coronate HL") Trimethylolpropane adducts of xylylene diisocyanate (for example, "Takenate D110N" made by Mitsui Chemicals, isocyanurate body of hexamethylene diisocyanate (for example, tosomer "coronate HX") Isocyanate addition product etc. are mentioned.

Examples of the epoxy crosslinking agent include bisphenol A, epichlorohydrin epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol. Glycidyl ether, trimethylolpropanetriglycidyl ether, diglycidyl aniline, diamineglycidylamine, N, N, N ', N'-tetraglycidyl-m-xylylenediamine and 1,3 -Bis (N, N- diglycidylaminomethyl) cyclohexane, etc. are mentioned.

The use amount in the case of using a crosslinking agent is not specifically limited, For example, it can be made into the quantity exceeding 0 weight part with respect to 100 weight part of polymer A. In some aspects, the usage-amount of the crosslinking agent with respect to 100 weight part of polymers A may be 0.01 weight part or more, 0.05 weight part or more, 0.1 weight part or more, 0.5 weight part or more, 1 weight part or more, for example. Or 1.5 parts by weight or more or 2 parts by weight or more. There exists a tendency for higher cohesion force to be obtained by increase of the usage-amount of a crosslinking agent. On the other hand, the amount of crosslinking agent used per 100 parts by weight of polymer A is usually suitably 15 parts by weight or less, and may be 10 parts by weight or less, and 5 parts by weight from the viewpoint of avoiding a decrease in tack due to excessive cohesion improvement. You may make it the following. Not too much usage of the crosslinking agent may be advantageous from the viewpoint of better expression of the use effect of the polymer B using the fluidity of the pressure-sensitive adhesive.

In order to advance a crosslinking reaction more effectively, you may use a crosslinking catalyst. Examples of the crosslinking catalyst include metal-based crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, nacer ferric iron, butyl tin oxide, and dioctyl tin dilaurate. Especially, tin type crosslinking catalysts, such as dioctyl tin dilaurate, are preferable. The amount of the crosslinking catalyst used is not particularly limited and can be, for example, approximately 0.0001 part by weight to 1 part by weight (typically 0.05 parts by weight or less) based on 100 parts by weight of polymer A.

A polyfunctional monomer can be used for an adhesive layer as needed. The polyfunctional monomer may be used for the purpose of adjusting the cohesive force by being used instead of the above-described crosslinking agent or in combination with the crosslinking agent. For example, in the adhesive layer formed of a photocurable adhesive composition, a polyfunctional monomer can be used preferably.

As the polyfunctional monomer, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycoldi ( Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexane Dioldi (meth) acrylate, 1,12-dodecanedioldi (meth) acrylate, trimethylolpropanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, allyl (meth) acrylate, vinyl (Meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl diol (meth) acrylate, hexyl diol di (meth) acrylate And the like can be mentioned. Especially, a trimethylol propane tri (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be used suitably. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

Although the usage-amount of a polyfunctional monomer changes with the molecular weight, the number of functional groups, etc., it is usually suitable to set it as about 0.01 weight part-about 3.0 weight part with respect to 100 weight part of polymers A. In some aspects, the usage-amount of a polyfunctional monomer may be 0.02 weight part or more with respect to 100 weight part of polymer A, and may be 0.03 weight part or more, for example. There exists a tendency for higher cohesion force to be obtained by increase of the usage-amount of a polyfunctional monomer. On the other hand, from a viewpoint of avoiding the fall of the tag by excessive cohesion improvement, the usage-amount of a polyfunctional monomer may be 2.0 weight part or less with respect to 100 weight part of polymer A, and may be 1.0 weight part or less, and 0.5 weight part or less. The fact that the amount of the polyfunctional monomer is not too high may be advantageous from the viewpoint of better expression of the use effect of the polymer B by using the fluidity of the pressure-sensitive adhesive.

(Adhesion imparting resin)

A tackifying resin can be contained in an adhesive layer as needed. Although it does not restrict | limit especially as tackifying resin, For example, rosin type tackifying resin, terpene tackifying resin, phenol type tackifying resin, hydrocarbon type tackifying resin, ketone type tackifying resin, polyamide type tackifying resin, Epoxy type tackifying resin, elastomer type tackifying resin, etc. are mentioned. Tackifying resin can be used individually by 1 type or in combination of 2 or more types.

In the aspect which includes a tackifying resin in an adhesive layer, content of this tackifying resin is not specifically limited, It can set so that appropriate adhesive performance may be exhibited according to an objective and a use. Content of tackifying resin with respect to 100 weight part of polymers A (when 2 or more types of tackifying resin is included, those total amounts) can be made into about 5 to 500 weight part, for example. In addition, in the technique disclosed here, the aspect whose content of tackifying resin with respect to 100 weight part of polymers A is less than 5 weight part, less than 2 weight part, or less than 1 weight part, or an adhesive layer does not contain tackifying resin substantially. Even if it does not carry out, it can implement preferably.

As tackifying resin, what softening point (softening temperature) is about 80 degreeC or more (preferably about 100 degreeC or more, for example, about 120 degreeC or more) can be used preferably. According to the tackifying resin which has a softening point more than the lower limit mentioned above, there exists a tendency for the initial stage low adhesiveness and the strong adhesiveness at the time of using a laminated body to improve effectively. The upper limit of the softening point is not particularly limited and may be, for example, about 200 ° C. or less (typically 180 ° C. or less). The softening point of tackifying resin can be measured based on the softening point test method (circulation method) prescribed | regulated to JISK2207.

(Formation of Adhesive Layer)

The adhesive layer 1 may be a hardened layer of an adhesive composition. That is, the pressure-sensitive adhesive layer 1 may be formed by applying a pressure-sensitive adhesive composition such as a water dispersion type, a solvent type, a photocurable type, or a hot melt type to a suitable surface, and then appropriately perform a curing treatment. When performing 2 or more types of hardening processes (drying | crosslinking, crosslinking, superposition | polymerization, cooling, etc.), these can be performed simultaneously or over several steps. In the adhesive composition using the partial polymer of a monomer component (acrylic-type polymer syrup), the final copolymerization reaction is typically performed as said hardening process. That is, the partial polymer is subjected to a new copolymerization reaction to form a complete polymer. For example, light irradiation is performed if it is a photocurable adhesive composition. If necessary, curing treatment such as crosslinking and drying may be performed. For example, when it is necessary to dry with a photocurable adhesive composition, you may perform photocuring after drying. In the adhesive composition using a complete polymer, typically, as said hardening process, processes, such as drying (heat drying) and crosslinking, are performed as needed.

Application | coating of an adhesive composition can be performed using common coaters, such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, and a spray coater. Application | coating of the adhesive composition and other adhesive composition used for formation of the adhesive layer 2 mentioned later can be performed similarly.

<A pressure sensitive adhesive layer formed of a photocurable composition containing a base polymer P and a photocuring agent>

The pressure-sensitive adhesive layer 2 contains a base polymer P and a photocuring agent, and exhibits a property of being cured by irradiation with actinic light (for example, UV) to improve adhesion. Using this property, for example, the adhesive force before photocuring is 2N / 25mm or less, and the sticking step, the cutting step, and some removing steps are performed before the photocuring, and then photocured to increase the adhesive force (typically, Is an aspect of raising to 5N / 25mm or more, and can be used suitably for implementation of the laminated body manufacturing method disclosed here. It is preferable that the adhesive composition (photocurable composition) which comprises the adhesive layer 2 contains the photoinitiator from a viewpoint of raising the efficiency of hardening by actinic light irradiation. From the viewpoint of hardening the pressure-sensitive adhesive layer before photocuring and suppressing the phenomenon in which the pressure-sensitive adhesive remains on the adherend, that is, the pressure-sensitive adhesive residual phenomenon, when the pressure-sensitive adhesive sheet in the second region is peeled off in the partial removal step. It is preferable that the crosslinked structure is introduced.

(Base polymer P)

As a base polymer P (Hereinafter, it may abbreviate as "polymer P") of the adhesive layer 2, an acryl-type polymer can be used preferably from a viewpoint of optical transparency. For example, it is preferable that 50 weight% or more of the adhesive layer 2 is an acrylic polymer. As an acryl-type polymer, 40 weight% or more in the constituent monomer components whole quantity can use preferably the same (meth) acrylic-acid alkylester as the polymer A mentioned above.

It is preferable that an acryl-type polymer contains the monomer component which has a crosslinkable functional group as a copolymerization component. As a monomer which has a crosslinkable functional group, a hydroxyl group containing monomer and a carboxy group containing monomer are mentioned. As an example of a hydroxyl-group containing monomer and a carboxyl group-containing monomer, the thing similar to the monomer illustrated as a structural monomer component of the polymer A contained in the adhesive layer 1 is mentioned. Especially, it is preferable to contain a hydroxyl group containing monomer. The hydroxyl group and carboxy group of the polymer P become a reaction point with the crosslinking agent mentioned later. By introducing a crosslinked structure into the polymer P, the cohesive force is improved, the adhesiveness of the pressure-sensitive adhesive layer 2 is improved, and the fluidity of the pressure-sensitive adhesive is lowered, so that the residual of the pressure-sensitive adhesive on the adherend in some removal steps tends to be reduced. have.

It is preferable that the total amount of the hydroxy group containing monomer and the carboxyl group-containing monomer with respect to constituent monomer component whole quantity is 1-30 weight%, It is more preferable that it is 3-25 weight%, and, as for an acryl-type polymer, it is further that it is 5-20 weight% desirable. It is preferable that especially content of the (meth) acrylic acid ester containing a hydroxyl group is the said range.

It is preferable that an acryl-type polymer contains a nitrogen containing monomer as a structural monomer component. As an example of a nitrogen containing monomer, the thing similar to the monomer illustrated as a structural monomer component of the polymer A contained in the adhesive layer 1 is mentioned. It is preferable that it is 1-30 weight%, as for content of the nitrogen containing monomer with respect to structural monomer component whole quantity, it is more preferable that it is 3-25 weight%, It is still more preferable that it is 5-20 weight%. It is preferable that an acryl-type polymer contains N-vinylpyrrolidone as said nitrogen-containing monomer in the said range.

When an acryl-type polymer contains both a hydroxyl group containing monomer and a nitrogen containing monomer as a monomer component, there exists a tendency for the cohesion force and transparency of an adhesive to become high. It is preferable that the total amount of the hydroxy group containing monomer and the nitrogen containing monomer with respect to constituent monomer component whole quantity is 5 to 50 weight%, It is more preferable that it is 10 to 40 weight%, More preferably, it is 15 to 35 weight% of an acryl-type polymer Do.

The acrylic polymer includes monomer components other than the above, for example, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy group-containing monomers, vinyl ether monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, acid anhydride group-containing monomers, and the like. You may include it.

It is preferable that content of the monomer of 40 degreeC or more of Tg of a homopolymer is 5-50 weight% with respect to the constituent monomer component whole quantity of the said acrylic polymer, and, as for an acryl-type polymer, it is more preferable that it is 10-40 weight%. From the viewpoint of suppressing the adhesive residue in the partial removal step, the constituent monomer component of the polymer P preferably includes a monomer component having a Tg of at least 80 ° C and a monomer component having a Tg of at least 80 ° C. It is more preferable to do. It is preferable that content of the monomer of Tg of a homopolymer with respect to constituent monomer component whole quantity is 0.1 weight% or more, It is more preferable that it is also 0.5 weight% or more, More preferably, it is 1 weight% or more of an acryl-type polymer It is especially preferable that it is 3 weight% or more. In particular, it is preferable that content of MMA is the said range. In addition, the suitable range of Tg of the acryl-type polymer used as polymer P may be the same as the suitable Tg of polymer A mentioned above.

Acrylic polymer can be obtained by well-known various polymerization methods similarly to the polymer A contained in the adhesive layer 1. For example, a solution polymerization method can be preferably employed.

The adhesive force of the adhesive layer before photocuring is easy to depend on the structural component and molecular weight of polymer P. From the viewpoint of achieving both suitable adhesiveness and suppression of adhesive residue in some removal steps, the weight average molecular weight of the acrylic polymer is preferably 100,000 to 5 million, more preferably 300,000 to 3 million, further 500,000 to 2 million desirable. In addition, when a crosslinked structure is introduce | transduced into the polymer P, the molecular weight of the polymer P refers to the molecular weight before introduction of a crosslinked structure.

(Bridge)

It is preferable that the crosslinked structure is introduce | transduced into the polymer P from a viewpoint of giving moderate cohesion force to an adhesive. For example, a crosslinking structure is introduce | transduced by adding a crosslinking agent to the solution after polymerizing polymer P, and heating as needed. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and a metal chelate crosslinking agent. These crosslinking agents react with functional groups, such as the hydroxyl group introduce | transduced into the polymer P, and form a crosslinked structure. As an isocyanate type crosslinking agent, the thing similar to the adhesive layer 1 can be used.

What is necessary is just to adjust the usage-amount of a crosslinking agent suitably according to the composition, molecular weight, etc. of polymer P. The amount of the crosslinking agent used may be, for example, about 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, still more preferably 1 to 4 parts by weight of the polymer P. Parts by weight. In order to promote formation of the crosslinked structure, a crosslinking catalyst may be used in the same manner as in the pressure-sensitive adhesive layer 1.

(Photocuring agent)

The adhesive composition which comprises the adhesive layer 2 is comprised so that photocurability may be shown by adding to the polymer P and containing a photocuring agent. The pressure-sensitive adhesive layer 2 exhibits a property of being photocured to improve adhesive strength by irradiating actinic rays as a stimulus for raising the adhesive force after bonding to the adherend.

As a photocuring agent, a photocurable monomer or a photocurable oligomer is used. As a photocuring agent, the compound which has two or more ethylenically unsaturated bonds in 1 molecule is preferable. Moreover, the compound in which the photocuring agent shows compatibility with the polymer P is preferable. It is preferable that a photocuring agent is a liquid at normal temperature from the point which shows suitable compatibility with the polymer P. Since the photocuring agent is compatible with the polymer P and uniformly dispersed in the composition, the contact area with the adherend can be ensured, and the pressure-sensitive adhesive layer 2 having high transparency can be formed.

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

It is preferable to use polyfunctional (meth) acrylate as a photocuring agent from the point of compatibility with an acryl-type polymer. As a polyfunctional (meth) acrylate, polyethyleneglycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, bisphenol Aethylene oxide modified di (meth) acryl Elate, bisphenol Apropylene oxide modified di (meth) acrylate, alkanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylic Late, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) a Relate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, butadiene (meth) acrylate, isoprene (meth) acrylate, etc. Can be mentioned.

The compatibility of the polymer P with the photocuring agent also depends on the molecular weight of the compound. The smaller the molecular weight of the photocurable compound, the higher the compatibility with the polymer P tends to be. From a compatibility viewpoint with the polymer P, 1500 or less are preferable and, as for the molecular weight of a photocuring agent, 1000 or less are more preferable.

The kind and content of a photocuring agent mainly affect the adhesive force after photocuring. The smaller the functional group equivalent (that is, the larger the number of functional groups per unit molecular weight), and the larger the content of the photocuring agent, the larger the adhesive force after photocuring tends to be.

From a viewpoint of raising the adhesive force after photocuring, 500 or less are preferable and, as for the functional group equivalent (g / eq) of a photocuring agent, 450 or less are more preferable. On the other hand, when the photocrosslinking density rises excessively, the viscosity of an adhesive may fall and adhesive force may fall. Therefore, 100 or more are preferable, as for the functional group equivalent of a photocuring agent, 130 or more are more preferable, 150 or more are more preferable, 180 or more are especially preferable.

In the combination of an acryl-type polymer and a polyfunctional acrylate photocuring agent, when the functional group equivalent of a photocuring agent is small, the interaction of polymer P and a photocuring agent tends to be strong, and there exists a tendency for the adhesive force before photocuring to become high. In the technique disclosed here, it is preferable that the functional group equivalent of a photocuring agent exists in the said range also from a viewpoint of suppressing the adhesive force before photocuring to an appropriate range, and improving the removability of the 2nd area | region in a some removal process.

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

When content of the photocuring agent in an adhesive composition becomes large, it will become easy to bleed out on the surface of an adhesive layer. When the photocuring agent bleeds out in large quantities, the photocuring agent tends to remain in the adherend after removing the second region. On the other hand, by bleeding out a small amount of the photocuring agent onto the surface, it becomes possible to suppress the adhesive force to the adherend of the pressure-sensitive adhesive layer and to make both the low tack before photocuring and the strong tack after photocuring suitably compatible.

(Photoinitiator)

It is preferable that the adhesive layer 2 contains a photoinitiator. The photoinitiator generates active species by irradiation of actinic rays, and accelerates the curing reaction of the photocuring agent. As a photoinitiator, a photocationic initiator (photoacid generator), a photoradical initiator, a photoanionic initiator (photobase generator), etc. are used according to the kind of photocuring agent. When polyfunctional acrylate is used as a photocuring agent, it is preferable to use an optical radical initiator. As an optical radical initiator, hydroxy ketones, benzyl dimethyl ketals, amino ketones, acyl phosphine oxides, benzophenones, trichloromethyl group containing triazine derivative, etc. are mentioned. An optical radical generating agent may be used independently, and may mix and use 2 or more types. 0.001-10 weight part is preferable with respect to 100 weight part of whole amounts of an adhesive layer, and, as for content of the photoinitiator in an adhesive layer, 0.01-5 weight part is more preferable.

(Other additives)

In addition to each component of the said example, an adhesive layer discloses additives, such as a silane coupling agent, a tackifier, a plasticizer, a softener, a deterioration inhibitor, a filler, a coloring agent, a ultraviolet absorber, antioxidant, surfactant, an antistatic agent, etc. here. You may contain in the range which does not largely impair the effect obtained by a technique.

(Formation of Adhesive Layer)

The pressure-sensitive adhesive layer 2 can be formed by, for example, applying a pressure-sensitive adhesive composition containing a polymer P, a photocuring agent, and other components used as necessary, to a suitable surface, and then drying and removing the solvent as necessary. As a drying method, a suitable and appropriate method can be adopted. Heat drying temperature becomes like this. Preferably it is 40 degreeC-200 degreeC, More preferably, it is 50 degreeC-180 degreeC, More preferably, it is 70 degreeC-170 degreeC. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, still more preferably 10 seconds to 10 minutes.

When an adhesive composition contains a crosslinking agent, it is preferable to advance bridge | crosslinking by heating or aging simultaneously with drying of a solvent or after drying of a solvent. Heating temperature and a heat time are suitably set according to the kind of crosslinking agent to be used, and a bridge | crosslinking is normally performed by heating for about 1 minute to about 7 days in 20 degreeC-160 degreeC. Heating for drying and removing the solvent may also serve as heating for crosslinking. Even after the crosslinking structure is introduced into the polymer by the crosslinking agent, the photocuring agent remains in an unreacted state. Therefore, the photocurable adhesive layer 2 containing the polymer P in which the crosslinked structure was introduce | transduced, and the unreacted photocuring agent is formed.

(Friction)

The pressure-sensitive adhesive layer 2 before photocuring has a frictional force at a frequency of 5 Hz measured by a tapping mode of a frictional force microscope (FFM), from the viewpoint of making it easy to suppress the adhesive force, from 2 to 5 times the frictional force at a frequency of 0.1 Hz. desirable. Moreover, when the ratio of the frictional force of the frequency of 0.1 Hz and 5 Hz of the adhesive layer 2 exists in the said range, it exists in the tendency for the adhesive force after photocuring to become large compared easily before photocuring.

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

The frictional force by nanofrictionology tends to reflect the adhesiveness to the surface adherend of the pressure-sensitive adhesive layer, and the small frictional force means that the surface of the pressure-sensitive adhesive is close to the liquid phase and has low tenacity. When the surface of an adhesive layer has viscosity, a frictional force becomes large and frequency dependence appears on the frictional force measured by FFM. While the frictional force measured at a particular frequency tends to reflect the individual physical properties of the components of the pressure-sensitive adhesive composition, the frequency dependence tends to more accurately reflect the surface properties. The smaller the frequency dependence of the frictional force, the smaller the viscosity and the stronger the liquid phase characteristics. The larger the frequency dependence of the frictional force, the higher the viscosity and the higher the adhesion to the adherend. For example, when the base polymer and the photocuring agent of the pressure-sensitive adhesive layer are not completely compatible, the liquid photocuring agent bleeds out to the surface, and a Weak Boundary Layer (WBL) is formed on the adhesive interface with the adherend. As the liquid phase becomes stronger, the frequency dependence of the friction force and friction force tends to be smaller.

By controlling the compatibility of the polymer P in the adhesive layer 2 and a photocuring agent, a small amount of photocuring agents may bleed out on the adhesive layer surface, and WBL may be formed. When the WBL is formed properly, the characteristics of the surface (adhesive interface) change, and the frequency dependence of the friction force and the friction force becomes small. Thereby, it becomes easy to suppress the adhesive force before photocuring, and peeling of the 2nd area | region in the case of performing a partial removal process before this photocuring becomes easy.

When the frictional force at the frequency of 5 Hz of the adhesive layer before photocuring is 5 times or less of the frictional force at the frequency of 0.1 Hz, there exists a tendency for peeling of the adhesive layer before a photocuring and a to-be-adhered body to become easy. From the viewpoint of avoiding bleed out of the photocuring agent, the frictional force at the frequency of 5 Hz of the pressure-sensitive adhesive layer is preferably two times or more, more preferably three times or more, and even more preferably 3.5 times or more.

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

From the viewpoint of increasing the adhesive force after photocuring, the adhesive layer after photocuring preferably has a frictional force at a frequency of 5 Hz measured by FFM at least 5 times, and more preferably at least 5.5 times the frictional force at a frequency of 0.1 Hz. The FFM differential signal at a frequency of 5 Hz of the pressure-sensitive adhesive layer after photocuring, measured using a cantilever having a spring constant of 40 N / m, is preferably 0.1 V or more, more preferably 0.2 V or more, and even more preferably 0.3 V or more. From a viewpoint of adhesive force improvement, the friction force of the adhesive layer after photocuring is so preferable that it is large. Therefore, the upper limit of the frictional force is not particularly limited, but the FFM differential signal at 5 Hz measured using a cantilever having a spring constant of 40 N / m is generally 10 V or less, and 5 V or less is preferable in consideration of the characteristic balance of the pressure-sensitive adhesive. Do.

As for the frictional force in the frequency 5Hz of the adhesive layer after photocuring, 1.5 times or more of the frictional force in the frequency 5Hz of the adhesive layer before photocuring is preferable, 2 times or more is more preferable, 2.5 times or more is still more preferable, 3 times The above is especially preferable. As the ratio of the frictional force before and after photocuring increases, the increase rate of the adhesive force due to photocuring tends to increase. The frictional force after photocuring is generally 20 times or less, and preferably 10 times or less of the frictional force before photocuring.

In addition, the frictional force at the frequency of 0.1 Hz and 5 Hz of the adhesive layer before and after photocuring is the FFM mode of a scanning probe microscope ("AFM5300E" by Hitachi Hi-Tech Science) under the following conditions, and the scan width of one direction is carried out. 5μm (10μm round trip) The measurement is performed by reading a differential voltage at a position of 3 占 퐉 from the left side of the measurement range.

(Measuring conditions)

Cantilever: "Tap300E-G" made by BudgetSensors (spring constant 40N / m equivalency product)

ADD value: 8.44 V, DIF value: 0.4 V, FFM value: 0 V

Atmosphere: vacuum, room temperature

Scan rate: 0.1 Hz, 1 Hz, and 5 Hz

As an example of the actinic light which can be used for photocuring of the adhesive layer 2, ultraviolet-ray (UV), visible light, an infrared ray, X-ray, (alpha) ray, (beta) ray, (gamma) ray, etc. are mentioned. UV is preferable as the actinic light from the viewpoint of easy curing of the pressure-sensitive adhesive layer in the storage state and easy curing. What is necessary is just to set irradiation intensity and irradiation time of an actinic light suitably according to the composition, thickness, etc. of an adhesive layer.

The adhesive layer 2 is photocurable, and can set the timing which raises adhesive force by hardening arbitrarily. Therefore, since a part removal process can be performed at arbitrary timings after attaching an adhesive sheet to a to-be-adhered body, until the adhesive is photocured, it can respond flexibly to the lead time of the manufacturing process of a device.

<Structure of Adhesive Sheet>

The thickness of the adhesive sheet used for the manufacturing method disclosed here is not specifically limited, For example, it may be about 3 micrometers-11 mm. From a viewpoint of the handleability of an adhesive sheet, etc., it is suitable that the thickness of an adhesive sheet is 5 micrometers or more normally, 10 micrometers or more may be sufficient and 30 micrometers or more may be sufficient as it. From some viewpoints, such as peeling workability of the 2nd area | region in a some removal process, in some aspects, the adhesive sheet whose thickness is 50 micrometers or more, 70 micrometers or more, or 90 micrometers or more can be used preferably. In addition, the thickness of an adhesive sheet should just be 1000 micrometers or less, for example, 600 micrometers or less, and 350 micrometers or less from a viewpoint of cutting workability in a cut process, peeling workability of the 2nd area | region in a part removal process, etc. 200 micrometers or less may be sufficient, and 150 micrometers or less may be sufficient as it.

In the adhesive sheet containing a base material layer and an adhesive layer, the thickness of an adhesive layer is not specifically limited, For example, it can be set as the range of about 1 micrometer-about 1000 micrometers. In some aspects, the thickness of an adhesive layer may be 3 micrometers or more, for example, may be 5 micrometers or more, 8 micrometers or more, 10 micrometers or more, 13 micrometers or more, 20 micrometers or more, or 20 micrometers or more may be sufficient. There exists a tendency for the laminated body which the adhesive piece bonded to the to-be-adhered body more firmly by the thickness increase of an adhesive layer. On the other hand, when the thickness of an adhesive layer is excessively large, workability | operativity (for example, separability of a 1st area | region and a 2nd area | region) in some removal processes by blocking of the adhesive of a 1st area | region and the adhesive of a 2nd area | region, etc. This may be a deterioration tendency. From such a viewpoint, the thickness of an adhesive layer may be 300 micrometers or less, for example, 200 micrometers or less, 150 micrometers or less, 100 micrometers or less, 70 micrometers or less, 50 micrometers or less, 40 30 micrometers or less may be sufficient as it.

In the adhesive sheet containing a base material layer and an adhesive layer, the thickness of a base material layer is not specifically limited, For example, it may be about 2 micrometers-about 10 mm. From the viewpoint of the handleability of the pressure-sensitive adhesive sheet and the prevention of breaking of the second region in the partial removal step, in some embodiments, the thickness of the base material layer may be, for example, 5 μm or more, or 10 μm or more, 25 It may be at least μm, may be at least 35 μm, may be at least 50 μm, or may be at least 60 μm. In addition, in several aspects, the thickness of a base material layer should just be 1000 micrometers or less, 500 micrometers or less, 300 micrometers or less, and 200 micrometers or less from a viewpoint of cutting workability in a cut process, etc. It may be sufficient, 150 micrometers or less, 100 micrometers or less, and 90 micrometers or less may be sufficient.

The adhesive sheet used for the manufacturing method disclosed here can be suitably implemented by the aspect whose thickness Ts of a base material layer is larger than the thickness Ta of an adhesive layer. That is, it is preferable that Ts / Ta is larger than one. Although not specifically limited, Ts / Ta may be 1.1 or more, 1.2 or more, 1.5 or more, 2 or more, or 2.5 or more may be sufficient as Ts / Ta, for example. In addition, Ts / Ta may be 50 or less, 20 or less, 10 or less, or 7 or less, for example. By using the adhesive sheet of the structure which satisfy | fills any upper limit mentioned above and / or satisfy | fills any lower limit mentioned above, favorable peeling workability in some removal processes and the adherend of the adhesive piece in the laminated body finally obtained are There is a tendency for good firm adhesion to each other.

In some aspects, the adhesive sheet used for a sticking process may have an area of 2500 cm <2> or more, for example, and the length of a short side may be 50 cm or more. In the aspect which uses the adhesive sheet of such a wide surface, it is especially meaningful to employ | adopt the manufacturing method disclosed here. By using such an adhesive sheet, there exists a tendency for one or two or more effects to be exhibited suitably among the improvement of positional precision, the improvement of shape precision, the improvement of productivity, etc., for example. Moreover, according to the manufacturing method disclosed here, since the partial removal process which peels and removes the 2nd area | region of the said adhesive sheet is performed before the adhesive force with respect to the to-be-adhered body of an adhesive sheet exceeds 2N / 25mm, a large surface as mentioned above Even in the adhesive sheet, it is easy to perform peeling removal of a 2nd area | region. According to the aspect whose area of the said adhesive sheet is 3600 cm <2> or more, More preferably, it is 4900 cm <2> or more, The aspect of the said short side is 60 cm or more, More preferably, 70 cm or more, a higher effect can be exhibited.

<Use>

According to the method disclosed here, the pattern by an adhesive piece is formed on a to-be-adhered body with high precision, and the laminated body excellent in the durability of the said pattern can be manufactured efficiently. Taking advantage of these features, the method disclosed herein includes products such as exterior materials and interior materials of vehicles, building materials such as exterior materials and interior materials of buildings, window glass, signs, signs, home appliances, optical products, electronic products, and components thereof. A to-be-adhered body can be preferably applied to the use which manufactures a laminated body partially covered by the pattern of an adhesive piece. The laminate may be the above-mentioned various products or its constituent members. Since the said adhesive piece is contained in various products as a component of the said laminated body, the adhering body contained in the said laminated body, the product containing the said laminated body, its member, decoration, display, protection, reinforcement, shock relief, It may be helpful to impart functions such as relaxation of stress concentration, shape retention, shape recovery, and the like. The method disclosed herein can be preferably applied, for example, to the production of FPC with a film coverlay.

Moreover, in the optical member used for an optical product, and the electronic member used for an electronic product, high integration, small size, light weight, and thinning are progressing, and several thin optical member / electronic member from which a linear expansion coefficient and thickness differ is laminated | stacked. Can be. By using such a member as a to-be-adhered body and forming a laminate in which the member is partially covered with an adhesive piece using the method disclosed herein, appropriate rigidity can be imparted to the optical member / electronic member. Thereby, in a manufacturing process and / or a product after manufacture, the curl and curvature which originate in the stress which may arise between the said several members of the said linear expansion coefficient or thickness can be suppressed.

Moreover, in the manufacturing process of an optical product / electronic product, in the state which performs shape processing processes, such as a cutting process, to a thin optical member / electronic member as mentioned above, the said member (adhered body) was partially covered with the adhesive piece. By forming a laminated body, using the said adhesive piece as a reinforcement member, local stress concentration to the optical member / electronic member accompanying processing of the said laminated body is alleviated, and a risk of a crack, a crack, peeling of a laminated member, etc. Can be reduced. Attaching and handling the reinforcing member to the optical member / electronic member also helps to alleviate local stress concentrations during conveyance, lamination, rotation, etc. of the member, and to suppress bending and bending due to the weight of the member. This can be

In addition, devices such as an optical product or an electronic product including a laminate in which the adherend is partially covered with the pattern of the pressure-sensitive adhesive piece are placed under heavy weight when the device falls in the stage used in the market for a consumer. Even when an unintentional stress is applied, such as when a flying object collides, the pressure-sensitive adhesive piece included in the device functions as a reinforcing member, so that the stress applied to the device can be alleviated and durability can be improved.

The method disclosed herein can be suitably used, for example, in order to make a laminated body, which is composed of components of various portable devices (portable devices) as an adherend, and the member is partially covered with a pattern of adhesive pieces. Here, "portable" means that simply being able to carry is not enough, and that a person (standard adult) has a level of portability that can be carried relatively easily. In addition, examples of the portable device referred to herein include a mobile phone, a smartphone, a tablet-type personal computer, a notebook computer, various wearable devices, a digital camera, a digital video camera, an acoustic device (walkman, IC recorder, etc.), a calculator (electronic calculator, etc.). ), Portable game devices, electronic dictionaries, electronic notebooks, electronic books, in-vehicle information devices, mobile radios, portable TVs, portable printers, mobile scanners, mobile modems, such as mechanical wristwatches and pocket watches, Flashlights, hand mirrors, and the like. Examples of the member constituting the portable electronic device may include an optical film, a display panel, or the like 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 here can be suitably applied also to the use which makes various members in automobiles, home appliances, etc. into a to-be-adhered body, and manufactures the laminated body in which this member was partly covered by the pattern of an adhesive piece.

Example

Hereinafter, although some Examples concerning this invention are described, it is not what intended limiting this invention to what is shown in this specific example. In addition, "part" and "%" in the following description are a basis of weight unless there is particular notice.

(Preparation of Polymer A1)

In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, 63 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of N-vinylpyrrolidone (NVP), methyl methacrylate (MMA) 9 13 parts of 2-hydroxyethyl acrylate (HEA) and 200 parts of ethyl acetate were added as a polymerization solvent, and after stirring for 2 hours at 60 ° C. under a nitrogen atmosphere, 0.2 parts of AIBN was added as a thermal initiator, and 6 parts at 60 ° C. Time reaction was performed and the solution of polymer A1 was obtained. Mw of this polymer A1 was 1.1 million.

(Preparation of Polymer A2)

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

(Preparation of Polymer A3)

96.2 parts of 2EHA, 3.8 parts of HEA and 150 parts of ethyl acetate as a polymerization solvent were put into a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, and stirred at 60 ° C. for 2 hours under a heat initiator. As an addition, 0.2 part of AIBN was added, and reaction was performed at 60 degreeC for 6 hours, and the solution (solid content 40%) of polymer A3 was obtained. Mw of this polymer A3 was 540,000.

(Preparation of Polymer B1)

40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), 20 parts of 2-ethylhexyl methacrylate (2EHMA), and functional group equivalents to a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube and a cooler 9 parts of 900g / mol polyorganosiloxane frame | skeleton containing methacrylate monomer (brand name: X-22-174ASX, the product made by Shin-Etsu Chemical Co., Ltd.), polyorganosiloxane frame | skeleton of functional equivalent is 4600g / mol 11 parts of methacrylate monomers (brand name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts of ethyl acetate and 0.6 parts of thioglycerol as a chain transfer agent were added, and the mixture was stirred at 70 ° C. under a nitrogen atmosphere for 1 hour. Thereafter, 0.2 part of AIBN was added as a thermal initiator and reacted at 70 ° C. for 3 hours, and then 0.1 part by weight of AIBN was further added, followed by reaction at 80 ° C. for 5 hours. Thus, the solution of siloxane structure containing polymer B1 was obtained. Mw of this polymer B1 was 20000.

In addition, the weight average molecular weight of each polymer mentioned above was measured on condition of the following using the GPC apparatus (made by Tosoh Corporation, HLC-8220GPC), and was calculated | required by polystyrene conversion.

Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)

Sample injection volume: 10 μl

Eluent: THF, flow rate: 0.6 ml / min

Measurement temperature: 40 ℃

·column:

Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)

Reference column; TSKgel SuperH-RC (1)

Detector: Differential Refractometer (RI)

<Production of adhesive sheet>

(Adhesive sheet D1)

To 100 parts of the polymer A1 contained in the solution in the solution of the polymer A1, 2.5 parts of the polymer B1 on a solids basis, an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylenediisocyanate, manufactured by Mitsui Chemical Corporation). ) 2.5 parts were added and mixed uniformly to prepare an adhesive composition C1.

The adhesive composition C1 was apply | coated directly to the single side | surface of 75-micrometer-thick PET film ("Lumier S10" made by Toray) which was not surface-treated, and it heated and dried at 110 degreeC for 2 minutes, and formed the adhesive layer of thickness 25micrometer. And the peeling process surface of the peeling liner (MRQ50T100 by Mitsubishi Chemical Corporation, the polyester film in which one side was treated with the silicone type peeling agent, 50 micrometers in thickness) were bonded and protected on the surface (adhesive surface) of this adhesive layer. Thus, the adhesive sheet D1 of the form which has an adhesive layer in the single side | surface of the base material layer which consists of PET films of thickness 75micrometer, and the surface (adhesive surface) of this adhesive layer was protected by the peeling liner was obtained.

(Adhesive sheet D2)

2.5 parts of isocyanate-based crosslinking agents (trade name: Takenate D110N, trimethylolpropanexylylene diisocyanate, manufactured by Mitsui Chemical Industries, Ltd.), based on solid content, per 100 parts of Polymer A1 contained in the solution, in the solution of Polymer A1. 30 parts of a chemical agent (brand name: A-200, polyethylene glycol # 200 diacrylate, functional group equivalent of 154 g / eq, Shinnakamura Kagaku Co., Ltd.) and 0.1 part of a photoinitiator are added, it is mixed uniformly, and the adhesive composition C2 is mixed. Prepared. As a photoinitiator, 1-hydroxycyclohexylphenyl ketone ("Irgacure 184" made from BASF) was used.

Thickness 25 by applying the adhesive composition C2 directly to one side of a 75-micrometer-thick PET film ("Lumier S10" made by Toray) without a surface treatment, using a fountain roll, and heating and drying at 130 degreeC for 1 minute. A pressure-sensitive adhesive layer was formed. A peeling treatment surface of a release liner (PET film treated with a silicone release agent, 25 μm in thickness) is bonded to the surface (adhesive surface) of the pressure-sensitive adhesive layer, and the crosslinking is performed by aging treatment for 4 days in an atmosphere of 25 ° C. Proceeded. Thus, the adhesive sheet D2 of the form in which the adhesive surface was protected by the peeling liner was obtained.

(Adhesive sheet D3)

To 100 parts of polymer A2 contained in the solution, 2.5 parts of isocyanate-based crosslinking agents (trade name: Takenate D110N, trimethylolpropanexylylene diisocyanate, manufactured by Mitsui Chemical Industries, Ltd.) were added to the solution of polymer A2 based on solid content, Evenly mixing to prepare pressure-sensitive adhesive composition C3. Except having used the adhesive composition C3 instead of the adhesive composition C1, it carried out similarly to manufacture of the adhesive sheet D1, and obtained the adhesive sheet D3 of the form whose adhesive surface was protected by the peeling liner.

(Adhesive sheet D4)

Except not using polymer B1, it carried out similarly to preparation of adhesive composition C1, and prepared adhesive composition C4. Except having used the adhesive composition C4 instead of the adhesive composition C1, it carried out similarly to manufacture of the adhesive sheet D1, and obtained the adhesive sheet D4 of the form in which the adhesive surface was protected by the peeling liner.

(Adhesive sheet D5)

To 100 parts of the polymer A3 contained in the solution, to the solution of the polymer A3, 2.5 parts of the polymer B1 based on solid content, isocyanate-based crosslinking agent (trade name: Coronate L (trimethylolpropane / tolylene diisocyanate trimer adduct 75) 3.3 parts of ethyl acetate solution, the Tosoh Corporation) was added, it mixed uniformly, and the adhesive composition C5 was prepared, except the adhesive composition C5 was used instead of the adhesive composition C1, and the adhesive surface was carried out similarly to manufacture of the adhesive sheet D1. Adhesive sheet D5 in the form protected with a release liner was obtained.

Measurement of Adhesion to Polyimide

The test piece for adhesive force measurement was produced by fixing the polyimide film ("Katon 50EN" made by Toray Dupont) of thickness 12.5 micrometers to a glass plate through a double-sided adhesive tape ("No.531" made by Nitto Denko). In addition, the adhesive sheets D1 to D4 and D5 were cut into a rectangle having a width of 25 mm to prepare a sample for measurement.

In the standard environment of 23 degreeC and 50% RH, the adhesive piece of the sample for a measurement was crimped | bonded by 2 reciprocating rollers to the said test piece. After leaving this for 30 minutes under the above standard environment, using a tensile tester ("TCM-1kNB" manufactured by Minebea Co., Ltd.), peeling strength (initial adhesive force) under conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min in accordance with JIS Z0237 ) B ₀ [N / 25mm] was measured.

Further, in the measurement of the initial adhesive strength B _0, and then compressing the sample for measurement on the test piece was allowed to stand to change the time under the standard environment of 12 and 24 hours. Other points were the same as the measurement of the initial adhesive force B ₀ , and the adhesive force [N / 25mm] after 12 hours of room temperature and the adhesive force [N / 25mm] after 24 hours of room temperature were measured.

In addition, the measurement sample was pressed on the test piece in the same manner as the measurement of the initial adhesive force B ₀ , and held for about 4 weeks under a fluorescent lamp at room temperature (about 25 ° C.), and then peeled off in the same manner as the measurement of the initial adhesive force B ₀ . Strength (adhesion after 4 weeks) [N / 25mm] was measured.

Further, the pressure-sensitive adhesive sheet D1, and then compressing the sample for measurement prepared from D5, in the same manner as in measurement of initial adhesive strength B ₀ in the test piece, and allowed to stand for 30 minutes in the standard atmosphere, was heated at 80 ℃ 5 minutes. Furthermore, after leaving for 30 minutes in the above standard environment, the peel strength (adhesion after heating) [N / 25mm] was measured under the conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min. It was 5.45 N / 25 mm in 25 mm and the adhesive sheet D5.

In addition, the measurement sample produced from the adhesive sheet D2 was pressed in the test piece in the same manner as in the measurement of the initial adhesive force B ₀ , and allowed to stand for 30 minutes under the above standard environment, followed by the use of UniField manufactured by Ushio Corporation. The 365 nm ultraviolet-ray was irradiated so that the light amount of 2000mJ / cm <2> may be sufficient. Moreover, after leaving for 30 minutes in the said standard environment, peeling strength (adhesive force after UV irradiation) [N / 25mm] was measured 19.84N / 25mm similarly on the conditions of 180 degree of peeling angles, and 300 mm / min of tensile velocity similarly.

<Production of Laminate>

(Manufacture example 1)

The adhesive sheet D1 was cut | disconnected to the size of width 25mm and length 100mm, and the adhesive sheet for laminated body manufacture was prepared. Moreover, as a to-be-adhered body, the polyimide film ("Kapton 50EN" by Toray Dupont Co., Ltd.) of thickness 12.5 micrometers, width 30mm, and length 120mm was prepared.

The center of the said to-be-adhered body and the center of the said adhesive sheet were aligned, and the said adhesive sheet was affixed on the to-be-adhered body by the hand roller (attaching process).

The cut process was performed after affixing an adhesive sheet to the said to-be-adhered body, and also before the following partial removal process. In the center of the width of the PSA sheet in the obtained PSA sheet / adhesive laminate, a second area having a width of 2 mm and a length of 100 mm extending linearly from one end in the long side direction of the PSA sheet to the other end is set, and the second The cutting process which cuts only adhesive sheet D1 was performed by irradiating a laser from an adhesive sheet surface side along the boundary (two straight lines) of an area | region and the 1st area | region of the both sides. The said cutting process was performed on condition of the following using the laser cutting device "Spirit, Model number SI-30V" by GCC Corporation.

Speed: 9.0%

Power: 10.0%

DPI: 500

PPI: 400

About 12 hours after attaching the adhesive sheet to the said to-be-adhered body, some removal processes were performed. Specifically, one end of the second region is peeled from the adherend and gripped with a chuck of a tensile tester, and is slit-shaped with a width of 2 mm by pulling in the longitudinal direction of the adhesive sheet under conditions of a peel angle of 180 degrees and a tensile speed of 300 mm / min. The second region of was peeled off from the adherend.

Subsequently, the above-mentioned heating (80 degreeC, 5 minutes) was performed as an adhesive force increase stimulus (adhesion force raising process), The laminated body of the objective, ie, the laminated body of the structure in which the said to-be-adhered body was covered with the said patterned adhesive sheet was produced. . In Table 1, the value of the adhesive force after 12 hours of room temperature of the adhesive sheet D1 is shown as the adhesive force at the time of the partial removal process of manufacture example 1, and the value of the adhesive force after heating of the adhesive sheet D1 is described as adhesive force of a laminated body.

(Manufacture example 2)

Production example except that the adhesive sheet D2 was used instead of the adhesive sheet D1, and the stimulus added in the adhesive force raising step was changed from heating to the above-described UV irradiation (about 365 nm wavelength, 2000 mJ / cm2 of light quantity). The laminate was prepared in the same procedure as in 1. In Table 1, the value of the adhesive force after 12 hours of room temperature of the adhesive sheet D2 as adhesive force at the time of the some removal process of manufacture example 2 is described, and the value of adhesive force after UV irradiation of the adhesive sheet D2 as adhesive force of a laminated body is described.

(Manufacture example 3, 4)

The standard mentioned above is not performed after heating process and UV irradiation mentioned above after each cut process using the adhesive sheet shown in Table 1, but instead, the elapsed time from the sticking of the adhesive sheet to a to-be-adhered body becomes 24 hours. It was left under the environment. In other respects, the laminate was produced in the same procedure as in Production Example 1. In Table 1, the value of the adhesive force after 12 hours of room temperature of each adhesive sheet is described as the adhesive force at the time of the partial removal process of manufacture examples 3 and 4, and the value of the adhesive force after 24 hours of room temperature of each adhesive sheet is described as adhesive force of a laminated body. .

(Manufacture example 5)

In Production Example 1, the above-described heating (80 ° C., 5 minutes) was performed about 11 hours after the adhesive sheet D1 was affixed to the adherend, and then the elapsed time after the adhesive sheet D1 was affixed to the adherend was about 12 hours. After keeping at room temperature until time, some removal process was performed. In other respects, the laminate was produced in the same manner as in Production Example 1. In Table 1, the value of the adhesive force after heating of the adhesive sheet D2 is described as adhesive force at the time of the some removal process of manufacture example 5.

(Manufacture example 6, 7)

In the same manner as in Production Example 1, the adhesive sheets D1 and D2 were affixed to the adherend, left in a room maintained in the above standard environment for about 24 hours under a fluorescent lamp, and then the cut process was performed in the same manner, followed by a partial removal process. . Then, the laminated body which concerns on manufacture examples 6 and 7 was obtained by hold | maintaining under pressure light in the room of the said standard environment until the elapsed time after sticking adhesive sheet D1, D2 to a to-be-adhered body for 4 weeks. In Table 1, the value of the adhesive force after room temperature of each adhesive sheet 24 hours as an adhesive force at the time of the partial removal process of manufacture examples 6 and 7, and the value of the adhesive force after 4 weeks of each adhesive sheet as adhesive force of a laminated body are described.

(Manufacture example 8)

A laminated body was manufactured by the procedure similar to the manufacture example 1 except the adhesive sheet D5 being used instead of the adhesive sheet D1. In Table 1, the adhesive force value after 12 hours of room temperature of the adhesive sheet D5 is shown as the adhesive force at the time of the some removal process of manufacture example 8, and the value of the adhesive force after heating of the adhesive sheet D5 is described as adhesive force of a laminated body.

(Slit removal evaluation)

In the part removal process of each manufacture example, when the 2nd area | region is peeled off from a to-be-adhered body, when deformation | transformation, such as elongation, is not confirmed by a to-be-adhered body, it is "G" (good pattern workability), and "P" when a deformation | transformation is confirmed. It evaluated as (the pattern workability is insufficient). The results are shown in Table 1.

In addition, in the manufacture examples 4 and 5, since the peeling of the 2nd area | region was not able to be performed suitably, the following durability tests were not performed. In addition, in any of Production Examples 1 to 3, 6, 7, and 8, no adhesive residue on the adherend or contamination of the adherend was observed at the time of peeling of the second region.

(Durability test)

For the laminate obtained in Production Examples 1 to 3, 6, 7, and 8, a planar no-load U-extension tester "DLDM111LH" and a jig (plane-shaped no-load U-extension test jig) manufactured by Yuasa System Co., Ltd. were used. Then, the durability test was carried out under the conditions of a stretching speed of 30 rpm, a bending radius of 3 mm, and stretching times of 100 times.

Specifically, as shown in FIG. 6, both ends x and y of the sample 60 are fixed to the clamp portions 61 and 62 of the tester with double-sided tape (not shown), and then the sample ( 60) The expansion and contraction which bend | folded by the U-shape of bending radius 3mm was performed repeatedly with the adhesive sheet side inward from the state of this plane. When bending the sample 60, both ends x and y of the sample 60 are brought into contact with each other by the operation of the clamp, while the other portions of the sample 60 are provided by the plate parts 63 and 64 separately provided. It picked up by no load from the outside.

The state of the sample after 100 expansion and contraction was visually observed and evaluated as "G" (good durability) when no lifting was observed between the adhesive sheet and the adherend, and "P" (lacking durability) when lifting was seen. It was. The results are shown in Table 1.

As shown in Table 1, of Production Examples 1, 2, 4 to 7, 8 regarding the production of a laminate having an adhesive force of 5 N / 25 mm, Production Example 1 in which a partial removal step was performed before the adhesive force exceeded 2 N / 25 mm. , 2, 6, 7, and 8 have good peelability of the second region in some removal steps, and the produced laminate exhibited good durability. Particularly good results were obtained in Production Examples 1, 2, 6, and 7 in which a laminate was manufactured using pressure-sensitive adhesive sheets D1 and D2 having a pressure-sensitive adhesive layer comprising polymer A1 copolymerized with N-vinyl cyclic amide. On the other hand, in the manufacture example 3, the laminated body obtained was low in durability, and in manufacture examples 4 and 5, the peelability of the 2nd area | region in some removal processes had difficulty.

As mentioned above, although the specific example of this invention was described in detail, these are only illustrations and do not limit a claim. The technique described in the claims includes various modifications and changes of the specific examples exemplified above.

In addition, the matter disclosed by this specification includes the following.

(1) It is a manufacturing method of the laminated body containing the to-be-adhered body and the adhesion piece which partially covers the to-be-adhered body, and the adhesive force with respect to the to-be-adhered body of the said adhesion piece is 5N / 25mm or more

A sticking step of attaching a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface on the adherend side of the base material layer to the adherend;

A cutting step of performing a cutting process on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece of the adhesive sheet; And,

A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;

, In this order,

Here, the said partial removal process is a laminated body manufacturing method performed before the adhesive force with respect to the to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm.

(2) The said laminated sheet manufacturing method as described in said (1) which uses the thing of 2 N / 25mm or less after adhesiveness after 24 hours at 23 degreeC, after bonding to a polyimide.

(3) The laminated body manufacturing method as described in said (1) or (2) which heat-processes after the said partial removal process and makes adhesive force with respect to the said to-be-adhered body of a said 1st area | region into 5 N / 25mm or more.

(4) The said adhesive layer is a laminated body as described in said (3) containing the polymer A whose glass transition temperature is less than 0 degreeC, and the polymer B which is a copolymer of the monomer which has a polyorganosiloxane skeleton, and a (meth) acrylic-type monomer. Manufacturing method.

(5) The laminated body manufacturing method as described in said (1) or (2) which performs ultraviolet irradiation process after the said partial removal process, and makes adhesive force with respect to the said to-be-adhered body of a said 1st area | region into 5 N / 25mm or more.

(6) The pressure-sensitive adhesive layer is made of a photocurable composition containing a base polymer and a photocuring agent,

The photocuring agent is a polyfunctional (meth) acrylate,

The laminated body manufacturing method as described in said (5) whose content of the said photocuring agent is 1 weight part or more and 50 weight part or less with respect to 100 weight part of said base polymers.

(7) The laminated body manufacturing method of said (1) or (2) stored after room temperature until the adhesive force with respect to the to-be-adhered body of a said 1st area | region becomes 5 N / 25mm or more after the said partial removal process.

(8) The laminated body in any one of said (1)-(7) whose thickness of the said adhesive sheet is 30 micrometers or more, and thickness Ts of the said base material layer is 2 times or more of the thickness Ta of the said adhesive layer. Manufacturing method.

(9) The said 2nd area | region is a laminated body manufacturing method in any one of said (1)-(8) set so that at least one end of the said 2nd area may reach the end of the said adhesive sheet.

The said 2nd area | region is a laminated body manufacturing method as described in said (9) whose one end which reaches the end of the said adhesive sheet becomes a shape which becomes wide toward the end of the said adhesive sheet.

(11) The laminated body manufacturing method in any one of said (1)-(10) whose said adhesive sheet used for the said sticking process is an area of 2500 cm <2> or more, and the length of a short side is 50 cm or more.

(12) As the said adhesive sheet and said to-be-adhered body used for the said pasting process, what includes the unit corresponding to the said laminated body is used,

The laminated body manufacturing method in any one of said (1)-(11) which further includes the division process which divides the said adhesive sheet and the to-be-adhered body into the said unit as a process performed after the said pasting process.

(13) It is an apparatus for implementing the manufacturing method in any one of said (1)-(12),

A sticking mechanism which affixes the said adhesive sheet,

Cut mechanism which performs cutting process to the said adhesive sheet,

Peeling mechanism for peeling off the second region of the pressure sensitive adhesive sheet

Laminated body manufacturing apparatus containing a.

1: laminate
10: adherend
10A: surface
20: adhesive sheet
21: first region
21A and 21B: Adhesive Piece
22: second area
202: substrate layer
204: adhesive layer
50: laminated body manufacturing apparatus
51: sticking mechanism
52: cut mechanism
53: peeling mechanism

Claims (10)

It is a manufacturing method of the laminated body containing the to-be-adhered body and the to-be-adhered body which partially adhered, and the adhesive force with respect to the to-be-adhered body of the said adhesion piece is 5 N / 25mm or more,
A sticking step of attaching a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface on the adherend side of the base material layer to the adherend;
A cutting step of performing a cutting process on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece of the adhesive sheet; And,
A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;
, In this order,
Here, the said adhesive layer contains the polymer A whose glass transition temperature is less than 0 degreeC, the polymer B which is a copolymer of the monomer which has a polyorganosiloxane skeleton, and a (meth) acrylic-type monomer,
The monomer component constituting the polymer A contains N-vinyl cyclic amide,
The said partial removal process is performed before the adhesive force with respect to the to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm,
The laminated body manufacturing method which heat-processes after the said partial removal process and makes the adhesive force with respect to the to-be-adhered body of a said 1st area | region into 5 N / 25mm or more. The method for producing a laminate according to claim 1, wherein the monomer component constituting the polymer A further contains a hydroxyl group-containing monomer. It is a manufacturing method of the laminated body containing the to-be-adhered body and the to-be-adhered body which partially adhered, and the adhesive force with respect to the to-be-adhered body of the said adhesion piece is 5 N / 25mm or more,
A sticking step of attaching a pressure-sensitive adhesive sheet including a base material layer and a pressure-sensitive adhesive layer laminated on at least the surface on the adherend side of the base material layer to the adherend;
A cutting step of performing a cutting process on the boundary between the first region constituting the adhesive piece and the second region not constituting the adhesive piece of the adhesive sheet; And,
A partial removal step of peeling and removing the second region from the adherend while leaving the first region on the adherend;
, In this order,
Here, an adhesive layer contains the polymer A whose glass transition temperature is less than 0 degreeC, and the polymer B which is a copolymer of the monomer which has a polyorganosiloxane skeleton, and a (meth) acrylic-type monomer,
The monomer component constituting the polymer A contains N-vinyl cyclic amide,
The said partial removal process is performed before the adhesive force with respect to the to-be-adhered body of the said adhesive sheet exceeds 2N / 25mm,
After the said partial removal process, the laminated body manufacturing method of storing at normal temperature until the adhesive force with respect to the to-be-adhered body of the said 1st area | region becomes 5 N / 25 mm or more. The laminated body manufacturing method in any one of Claims 1-3 in which the adhesive force after 24 hours progresses at 23 degreeC after bonding to a polyimide as said adhesive sheet is used. The laminated body manufacturing method of any one of Claims 1-4 whose thickness of the said adhesive sheet is 30 micrometers or more, and thickness Ts of the said base material layer is 2 times or more of the thickness Ta of the said adhesive layer. The said 2nd area | region is a laminated body manufacturing method in any one of Claims 1-5 set so that at least one end of the said 2nd area may reach the end of the said adhesive sheet. The said 2nd area | region is a laminated body manufacturing method of Claim 6 whose shape which the width | variety which reaches the end of the said adhesive sheet becomes wide toward the end of the said adhesive sheet. The said adhesive sheet used for the said sticking process has an area of 2500 cm <2> or more, and the length of a short side is 50 cm or more in the laminated body manufacturing method in any one of Claims 1-7. The said adhesive sheet and the to-be-adhered body which are used for the said pasting process are used, The thing in which two or more units corresponding to the said laminated body is used is used, The said any one of Claims 1-8.
The laminated body manufacturing method further including the division process which divides the said adhesive sheet and the to-be-adhered body into the said unit as a process performed after the said pasting process. It is an apparatus for implementing the manufacturing method in any one of Claims 1-9.
A sticking mechanism which affixes the said adhesive sheet,
Cut mechanism which performs cutting process to the said adhesive sheet,
Peeling mechanism for peeling off the second region of the pressure sensitive adhesive sheet
Laminated body manufacturing apparatus containing a.

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