JP2018115310A - Manufacturing method of size enlarged adhesive sheet laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To propose a novel manufacturing method of a size enlarged adhesive sheet laminate having an adhesive material layer and a coating part I detachably laminated on one surface of the adhesive material layer and a constitution by size enlargement of an adhesive material layer uneven surface part on one surface of the adhesive material, capable of forming the adhesive material layer uneven surface part matching to uneven part of an adhesive surface on an adhesive material layer surface with high accuracy.SOLUTION: There is proposed a novel manufacturing method of a size enlarged adhesive sheet laminate by heating an adhesive sheet laminae and molding a heated adhesive sheet laminate and cooling the same, including heating the adhesive sheet laminate to initiate molding at a state that storage elastic modulus E' (MS) of a coating part I of 1.0×10to 2.0×10Pa and finalize molding at a state that storage elastic modulus E' (MF) of a coating part I is 5.0×10to 1.0×10Pa.SELECTED DRAWING: Figure 2

Description

  The present invention can be suitably used for forming an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet. The present invention relates to a method for producing an adhesive sheet laminate.

A touch panel image display device is usually configured by combining a surface protection panel, a touch panel, and an image display panel (collectively, also referred to as “component for image display device”).
In recent years, surface protection panels for touch panel image display devices such as smartphones and tablet terminals have been made of tempered glass and plastic materials such as acrylic resin plates and polycarbonate plates. The part is printed in black.
In the touch panel, a plastic film sensor is used together with the glass sensor, a touch-on lens (TOL) member in which the touch panel function is integrated with the surface protection panel, or the touch panel function is integrated in the image display panel. Members such as on-cell and in-cell are used.

In this type of image display device, in order to further improve the image visibility, the gaps between the constituent members for each image display device are made of a transparent resin such as a liquid adhesive, a thermoplastic adhesive sheet material, and an adhesive sheet material. The structure to fill is common.
By the way, in the field of image display devices centering on mobile phones and mobile terminals, in addition to thinning and high precision, design diversification has progressed, and the peripheral edge of the surface protection panel has a black frame shape. In the past, it has been common to print the concealing portion, but with the diversification of design, the frame-shaped concealing portion has begun to be formed in a color other than black. When the concealing part is formed with a color other than black, the concealing property is low, and therefore the height of the concealing part, that is, the printing part tends to be higher than that of black. Therefore, it is required that the pressure-sensitive adhesive sheet for laminating components having such a printing unit be filled to every corner following a large printing step.
Therefore, various methods for filling the printing step have been proposed.

  For example, Patent Document 1 discloses a new image display device that can be bonded to a surface to be adhered in a close contact state even if the surface to be bonded to which the pressure-sensitive adhesive sheet is bonded has a step due to printing or the like. A double-sided pressure-sensitive adhesive sheet for bonding any two adherends selected from the constituent members for image display devices of a surface protection panel, a touch panel and an image display panel as a double-sided pressure-sensitive adhesive sheet, The body has a stepped portion on the adherend surface to which the double-sided pressure-sensitive adhesive sheet is adhered, and the double-sided pressure-sensitive adhesive sheet has a shape of a bonding surface to be bonded to the adherend surface along the surface shape of the adhesion surface. A double-sided pressure-sensitive adhesive sheet for an image display device, which is shaped, is disclosed.

  Moreover, in patent document 2, about the manufacturing method of the double-sided adhesive sheet for bonding any two adherends selected from a surface protection panel, a touch panel, and an image display panel, the double-sided adhesive sheet before bonding is A double-sided pressure-sensitive adhesive sheet for an image display device, wherein the pressure-sensitive adhesive composition having a gel fraction of less than 40% is formed into the same surface shape as the uneven shape of the bonding surface of the adherend. A manufacturing method is disclosed.

WO2014 / 073316 A1 WO2015 / 174392 A1

  In recent years, in the field of image display devices centering on mobile phones and mobile terminals, there has been a further demand for thinning and high precision, and adhesive sheets for bonding image display device components also have printing steps and the like. It is required that the uneven portion on the surface of the adherend can be filled with high accuracy and that the adhesive material does not protrude outside. As a countermeasure for this, it has been studied that the surface shape of the pressure-sensitive adhesive sheet is formed in advance along the surface shape of the adherend as disclosed in the above-mentioned prior patent documents.

And in order to form the surface shape of the pressure-sensitive adhesive sheet in advance along the surface shape of the adherend, press-molding a pressure-sensitive adhesive sheet laminate in which release sheets are laminated on both sides of the pressure-sensitive adhesive sheet. Thus, a method of forming a concavo-convex shape coinciding with the concavo-convex portion on the adherend surface is assumed.
However, as a result of actually carrying out the method using a pressure-sensitive adhesive sheet laminate formed by laminating a normal release sheet on both sides of the pressure-sensitive adhesive sheet, a concavo-convex shape coinciding with the concavo-convex portion on the adherend surface is obtained. The problem that it is difficult to form on the surface of an adhesive sheet with high accuracy has been clarified.

  Therefore, the present invention includes an adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer, and a concave portion, a convex portion, or an uneven portion (“adhesive material layer” is provided on one surface of the adhesive material. The pressure-sensitive adhesive layer surface irregularities matching the irregularities on the surface of the adherend with high accuracy are disclosed. The present invention proposes a new method for producing a shaped pressure-sensitive adhesive sheet laminate which can be formed on the surface and preferably can be continuously produced.

The present invention comprises an adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer. One surface of the adhesive material has a concave portion, a convex portion, or an uneven portion ("adhesive material layer surface"). In the manufacturing method of the shaped pressure-sensitive adhesive sheet laminate having a structure formed by shaping the concavo-convex part),
The pressure-sensitive adhesive layer is provided with an adhesive material layer and a covering portion I that is detachably laminated on one surface of the pressure-sensitive adhesive material layer, and the heated pressure-sensitive adhesive sheet laminate is formed and cooled to form pressure-sensitive adhesive. A manufacturing method for manufacturing a sheet laminate,
The pressure-sensitive adhesive sheet laminate is heated, and molding is started in a state where the storage elastic modulus E ′ (MS) of the covering part I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and the covering part I is stored. A new method for producing a shaped pressure-sensitive adhesive sheet laminate is proposed in which molding is terminated in a state where the elastic modulus E ′ (MF) is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa.

  The present invention further proposes a method for producing a new shaped pressure-sensitive adhesive sheet laminate, wherein the heated pressure-sensitive adhesive sheet laminate is molded using a cooled mold.

According to the method for producing a shaped pressure-sensitive adhesive sheet laminate proposed by the present invention, for example, after heating the pressure-sensitive adhesive sheet laminate, the covering portion I starts forming in a predetermined state, and the covering portion I is predetermined. By finishing the molding in the state, it is possible to form an uneven shape coincident with the uneven portion on the surface of the adherend with high accuracy on the surface of the adhesive material layer.
Furthermore, when the heated pressure-sensitive adhesive sheet laminate is molded, if it is molded using a cooled mold, it can be cooled at the same time as the molding, and the process can be completed simultaneously. Can do.

It is sectional drawing which showed typically an example of the adhesive sheet laminated body which is an Example of this invention. It is sectional drawing for demonstrating an example of the press process at the time of manufacturing a shaped adhesive sheet laminated body using an example of the adhesive sheet laminated body which is an Example of this invention. It is the figure which showed typically an example of the shaped adhesive sheet laminated body which is an Example of this invention, (A) is sectional drawing, (B) is a perspective view. It is the figure which showed the viscoelastic curve of the material (coating part I) used for the adhesive sheet laminated body produced by the Example and the comparative example. It is the figure which showed the viscoelastic curve of the material (adhesive layer) used for the adhesive sheet laminated body produced by the Example and the comparative example. It is the perspective view which showed one side of the metal mold | die used by the Example and the comparative example.

  An example of the embodiment of the present invention will be described below. However, the present invention is not limited to the following embodiment.

[This manufacturing method]
The method for producing a shaped pressure-sensitive adhesive sheet laminate (referred to as “the present production method”) according to an example of the present embodiment heats the pressure-sensitive adhesive sheet laminate described later (heating step) and forms the heated pressure-sensitive adhesive sheet laminate. And a cooling method (molding / cooling step).

  As long as the manufacturing method includes the heating step and the molding / cooling step, the manufacturing method may include other steps. For example, you may provide processes, such as a heat treatment process, a conveyance process, a slit process, and a cutting process, as needed. However, it is not limited to these processes.

<Adhesive sheet laminate>
The pressure-sensitive adhesive sheet laminate as a starting member in the present production method only needs to include the pressure-sensitive adhesive layer and the covering portion I that is detachably laminated on one surface of the pressure-sensitive adhesive layer, and includes other members. May be. For example, as shown in FIG. 1, an adhesive material layer, a covering portion I that is detachably laminated on one side of the adhesive material layer, and a peelable laminate on the other side of the adhesive material layer. A pressure-sensitive adhesive sheet laminate provided with the covering portion II can be exemplified. However, whether or not the covering portion II is provided is arbitrary, and the covering portion II may not be stacked.
In addition, the detail of an adhesive sheet laminated body is mentioned later.

<Heating process>
In this manufacturing method, it is preferable that the pressure-sensitive adhesive sheet laminate is heated so that the storage elastic modulus E ′ (M) of the covering portion I is in a state of 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa. .
If the storage elastic modulus E ′ (M) of the covering portion I is in the above range, the covering portion I can be deformed to an extent suitable for molding, and a desired uneven shape is accurately formed on the surface of the adhesive layer. It can be shaped.
From this point of view, it is preferable that the pressure-sensitive adhesive sheet laminate is heated so that the storage elastic modulus E ′ (M) of the covering portion I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa. 5.0 × 10 ⁶ Pa or more or 1.0 × 10 ⁹ Pa or less, more preferably 1.0 × 10 ⁷ Pa or more or 5.0 × 10 ⁸ Pa or less.

  Here, in order to adjust the storage elastic modulus E ′ (M) of the covering portion I within the above range by heating the pressure-sensitive adhesive sheet laminate, the components and gel components of the composition constituting the covering portion I can be adjusted. It can adjust by adjusting heating temperature according to a rate, a weight average molecular weight, etc. However, it is not limited to this method.

Furthermore, the said adhesive sheet laminated body is heated, the storage elastic modulus E '(M) of the coating | coated part I is 1.0 * 10 < ⁶ > -2.0 * 10 < ⁹ > Pa, And the storage elasticity of an adhesive material layer It is even more preferable that the rate G ′ (S) is less than 1.0 × 10 ⁴ Pa.
If the storage elastic modulus E ′ (M) of the covering portion I is adjusted to the above range, the above-described effects can be obtained, and in addition, the storage elastic modulus G ′ (S) of the adhesive layer is 1. If it is less than 0 * 10 < ⁴ > Pa, sufficient moldability can be provided to an adhesive material layer.
From this viewpoint, the pressure-sensitive adhesive sheet laminate is heated so that the storage elastic modulus E ′ (M) of the covering portion I is in the above range, and the storage elastic modulus G ′ (S) of the pressure-sensitive adhesive layer is 1. In a state of less than 0.0 × 10 ⁴ Pa, particularly in a state of 5.0 × 10 ¹ Pa or more or 5.0 × 10 ³ Pa or less, in particular, 1.0 × 10 ² Pa or more or 1.0 × 10 ³ It is preferable to be in a state of Pa or less.

  Here, the storage elastic modulus G ′ (S) of the pressure-sensitive adhesive layer is adjusted by adjusting the heating temperature according to the components, gel fraction, weight average molecular weight, etc. of the composition constituting the pressure-sensitive adhesive layer. Can do. However, it is not limited to this method.

Furthermore, it is particularly preferable to heat the pressure-sensitive adhesive sheet laminate so that the value of the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 or more. The loss tangent tan δ will be described later.
If the value of the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 or more, it is preferable that the adhesive material layer is flexible enough to be molded.
From this point of view, it is particularly preferable to heat the pressure-sensitive adhesive sheet laminate so that the value of the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 or more. More preferably, it is 3.0 or more or 10 or less. However, the upper limit is not limited to this.

In this manufacturing method, it is preferable to heat the pressure-sensitive adhesive sheet laminate so that the surface temperature of the covering portion I is 70 to 180 ° C.
If the surface temperature of the covering portion I is 70 ° C. or higher, the adhesive layer can be sufficiently softened and the covering portion I can be sufficiently deformed. This is preferable because it can suppress adverse effects such as generation of heat and decomposition of the adhesive layer due to heat.
From this point of view, it is preferable to heat the pressure-sensitive adhesive sheet laminate so that the surface temperature of the covering portion I is 70 to 180 ° C., among which 75 ° C. or more or 150 ° C. or less, among which 80 ° C. or more or 120 It is even more preferable that the temperature is not higher than ° C.

  As a method for heating the pressure-sensitive adhesive sheet laminate, for example, a method of heating the pressure-sensitive adhesive sheet laminate from above and below between upper and lower heating plates provided with a heating body such as an electric heater, a method of directly sandwiching with a heating plate, The method using a heating roll, the method of immersing in hot water, etc. can be mentioned. However, it is not limited to these methods.

<Molding / cooling process>
In this step, the pressure-sensitive adhesive sheet laminate heated as described above is formed, and the pressure-sensitive adhesive sheet laminate is formed and cooled. That is, the pressure-sensitive adhesive sheet laminated body in a state where the pressure-sensitive adhesive layer and the covering portion I are laminated and integrated is formed as it is. Therefore, the covering portion I is formed by the mold, and the adhesive material layer is also simultaneously formed through the covering portion I.

  In this step, the heated pressure-sensitive adhesive sheet laminate may be molded and then cooled, or may be cooled simultaneously with the molding. For example, by pressing with a cooled mold, molding and cooling can be performed simultaneously and completed simultaneously. Thereby, this manufacturing method can be continuously implemented so that it may mention later.

  As a molding method, the molding method is not particularly limited as long as the uneven shape can be formed integrally with the pressure-sensitive adhesive sheet laminate. For example, press molding, vacuum forming, pressure forming, shaping by a roll, compression molding, shaping by lamination and the like can be mentioned. Among these, press molding is particularly preferable from the viewpoints of moldability and workability.

The material of the mold is not particularly limited. For example, resin-based materials such as silicone resin and fluororesin, and metal-based materials such as stainless steel and aluminum can be used. Among these, metal molds that can be controlled in temperature during molding are particularly preferred because high-precision moldability is required for forming irregularities on the adherend.
As the mold cooling means, a usual cooling means can be adopted. For example, cooling means by water cooling or compressed air can be mentioned.

  For example, as shown in FIG. 2, the mold is a bonding surface of an adherend that adheres a predetermined uneven shape, for example, an adhesive material layer, to the inner wall surface of at least one of the pair of molds to be opened and closed. By providing a concave / convex shape coincident with the concave or convex portion or the concave / convex portion (also referred to as “bonding surface”), the pressure-sensitive adhesive sheet laminate is press-molded, vacuum-molded, compressed-air molded or rolled using the mold. By forming, the uneven shape can be transferred to the pressure-sensitive adhesive sheet laminate and shaped.

In this step, as described above, molding is started in a state where the storage elastic modulus E ′ (MS) of the covering portion I in the pressure-sensitive adhesive sheet laminate is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa. Is preferred.
Here, “start molding” means, for example, in the case of molding using a mold, closes the mold, that is, starts pressing the adhesive sheet laminate with the mold.

If the storage elastic modulus E ′ (MS) of the covering portion I is in the range of 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, the covering portion I can be deformed to an extent suitable for molding, In addition, a desired uneven shape can be accurately formed on the surface of the adhesive layer.
From this point of view, it is preferable to start forming the pressure-sensitive adhesive sheet laminate in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa. It is even more preferable to start molding in a state of 0.0 × 10 ⁶ Pa or more or 1.0 × 10 ⁹ Pa or less, in particular, a state of 1.0 × 10 ⁷ Pa or more or 5.0 × 10 ⁸ Pa or less. preferable.

Furthermore, the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and the storage elastic modulus G ′ (SS) of the adhesive layer is 1.0. It is even more preferable to start forming the pressure-sensitive adhesive sheet laminate in a state of less than × 10 ⁴ Pa.
In addition to being able to obtain the effects described above if molding is started in a state where the storage elastic modulus E ′ (MS) of the covering portion I is within the above range, the storage elastic modulus G ′ (SS) of the adhesive layer ) Starts in a state of less than 1.0 × 10 ⁴ Pa, the pressure-sensitive adhesive layer can be formed in a state having more sufficient formability.
From this point of view, the storage elastic modulus E ′ (MS) of the covering portion I is in the above range, and the storage elastic modulus G ′ (SS) of the adhesive layer is less than 1.0 × 10 ⁴ Pa. More preferably, the G ′ (SS) is 5.0 × 10 ¹ Pa or more or 5.0 × 10 ³ Pa or less, more preferably 1.0 × 10 ² Pa or more or 1.0 × 10. ^It is even more preferable to start molding in a state of ³ Pa or less.

Moreover, it is preferable to start molding in a state where the surface temperature of the covering portion I is 70 to 180 ° C.
If the surface temperature of the covering portion I is 70 ° C. or higher, the adhesive layer is sufficiently softened and the covering portion I can be sufficiently deformed. This is preferable because generation of wrinkles and decomposition of the adhesive layer due to heat can be suppressed.
Therefore, it is preferable to start the molding in a state where the surface temperature of the covering portion I is 70 to 180 ° C., among which 75 ° C. or more or 150 ° C. or less, particularly 80 ° C. or more and 120 ° C. or less. Even more preferred.

On the other hand, in this step, it is preferable to finish the molding in a state where the storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa.
Here, “finishing the molding” means ending the molding pressure on the pressure-sensitive adhesive sheet laminate, and means that the mold is opened if molding is performed.

If the storage elastic modulus E ′ (MF) of the covering portion I is in the range of 5.0 × 10 ⁷ Pa to 1.0 × 10 ¹⁰ Pa, it is preferable because the shape stability after molding is excellent.
From such a viewpoint, it is preferable to finish the molding in a state where the storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa, and in particular, 1.0 × 10 It is even more preferable to finish the molding in a state of ⁸ Pa or more or 8.0 × 10 ⁹ Pa or less, in particular, a state of 1.0 × 10 ⁹ Pa or more or 5.0 × 10 ⁹ Pa or less.

Furthermore, it is molded in a state where the storage elastic modulus E ′ (MF) of the covering portion I is in the above range and the storage elastic modulus G ′ (SF) of the adhesive layer is 1.0 × 10 ⁴ Pa or more. It is even more preferable to end the process.
In addition to obtaining the above-described effects if the molding is completed in a state where the storage elastic modulus E ′ (MF) of the covering portion I is within the above range, the storage elastic modulus G ′ ( If molding is finished in a state where SS) is 1.0 × 10 ⁴ Pa or more, the molded pressure-sensitive adhesive layer can maintain its shape.
From this viewpoint, the storage elastic modulus E ′ (MF) of the covering portion I is in the above range, and the storage elastic modulus G ′ (SF) of the adhesive layer is 1.0 × 10 ⁴ Pa or more. It is preferable to finish the molding, and among them, the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 5.0 × 10 ⁴ Pa or more or 5.0 × 10 ⁷ Pa or less. More preferably, the molding is finished in a state of x10 ⁴ Pa or more or 1.0 x 10 ⁷ Pa or less.

Further, it is preferable to finish the molding in a state where the surface temperature of the covering portion I is less than 50 ° C. For example, in the case of press molding, it is preferable to open the mold while the surface temperature is less than 50 ° C.
If the surface temperature of the covering portion I is less than 50 ° C. and the storage elastic modulus E ′ (MS) of the covering portion I is in the range of 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa, the molded body after the completion of molding This is preferable because it can be prevented from being deformed when the material is taken out and warping due to thermal contraction of the covering portion I can be suppressed.
From this point of view, the molding is finished in a state where the surface temperature of the covering portion I is less than 50 ° C., particularly in a state where the surface temperature is 0 ° C. or more or 45 ° C. or less, and in particular, in a state where it is 10 ° C. or more or 40 ° C. Is preferred.

Furthermore, the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding and the storage elastic modulus E ′ (MF) of the covering portion I at the end of forming satisfy the following relational expression (1). preferable.
(1) E '(MF) / E' (MS) ≧ 1.3
Here, if the storage elastic modulus E ′ (MS) of the covering portion I and the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding satisfy the relational expression (1), the molding is started at the start of molding. It is preferable because it is as soft as possible and has hardness to the extent that the molded shape can be maintained after completion of molding.
From this point of view, it is preferable that E ′ (MF) / E ′ (MS) ≧ 1.3. Above all, 100 ≧ E ′ (MF) / E ′ (MS) or E ′ (MF) / E ′ (MS ) ≧ 3.0, more preferably 50 ≧ E ′ (MF) / E ′ (MS) or E ′ (MF) / E ′ (MS) ≧ 5.0. However, the upper limit of E ′ (MF) / E ′ (MS) is not limited to this.

Further, the storage elastic modulus E ′ (MF) of the covering portion I at the end of the molding and the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer at the end of the molding satisfy the following relational expression (2). Is preferred.
(2) .. E ′ (MF) / G ′ (SF) ≦ 1.0 × 10 ⁷
Here, if the storage elastic modulus E ′ (MF) of the covering portion I at the end of the molding and the storage elastic modulus G ′ (SF) of the adhesive layer at the end of the molding satisfy the relational expression (2). The formed pressure-sensitive adhesive layer can maintain its shape.
From this viewpoint, it is preferable that E ′ (MF) / G ′ (SF) ≦ 1.0 × 10 ⁷ , and 1.0 ≦ E ′ (MF) / G ′ (SF) or E ′ (MF) among them. /G′(SF)≦5.0×10 ⁶ , of which 1.0 × 10 ¹ ≦ E ′ (MF) / G ′ (SF) or E ′ (MF) / G ′ (SF) ≦ 1.0 More preferably, it is × 10 ⁶ .

  Again, in this manufacturing method, the mold may be press-molded and cooled after the mold is opened, or the mold may be cooled and cooled at the same time as the press molding. If the mold is cooled in this way and cooled at the same time as the press molding, the cooling can be completed at the same time as the molding. Therefore, since the shaped pressure-sensitive adhesive sheet laminate can be conveyed to the next step immediately after the molding and cooling are completed, the shaped pressure-sensitive adhesive sheet laminate can be continuously produced.

When cooling at the same time as the mold forming, the surface temperature of the mold is preferably 0 to 50 ° C.
If the surface temperature of the mold is 50 ° C. or less, the shape of the pressure-sensitive adhesive sheet laminate can be fixed in a short time, the resulting molded body is accurate, and warps due to thermal shrinkage in the cooling process after molding. It is preferable from the viewpoint of suppression.
Therefore, the surface temperature of the mold is preferably 0 to 50 ° C., more preferably 10 ° C. or more and 40 ° C. or less, and more preferably 15 ° C. or more and 30 ° C. or less.

  In addition, conditions concerning press molding such as a press pressure and a press time are not particularly limited, and may be appropriately adjusted depending on a dimension and shape to be molded, a material to be used, and the like.

<Others>
The shaped pressure-sensitive adhesive sheet laminate obtained in the molding / cooling step may be wound up as it is, heat-treated, or cut into a predetermined size and shape.
When cutting, for example, a cutting method using a Thomson blade or a rotary blade can be used.

In this production method, it is preferable to continuously produce a shaped pressure-sensitive adhesive sheet laminate.
For example, the pressure-sensitive adhesive sheet laminate is transported to a heating unit such as a heater, and the heating unit stops the transport for a predetermined time and heats it while heating or while transporting, and then heats the pressure-sensitive adhesive sheet laminate to a molding unit. For example, it is transferred to a molding die, and in the molding unit, for example, a cooled die is pressed and cooled at the same time as molding, and further transported to the next unit as necessary. A shaped pressure-sensitive adhesive sheet laminate can be produced.

[This adhesive sheet laminate]
Next, a suitable example of the pressure-sensitive adhesive sheet laminate used in the production method (referred to as “the pressure-sensitive adhesive sheet laminate”) will be described.

  As shown in FIG. 1, the pressure-sensitive adhesive sheet laminate is peeled off from the pressure-sensitive adhesive layer, the covering portion I that is detachably laminated on the front and back sides of the pressure-sensitive adhesive layer, and the other side of the pressure-sensitive adhesive layer. It is a pressure-sensitive adhesive sheet laminate including a covering portion II that can be laminated. Whether or not the covering portion II is provided is arbitrary.

<Adhesive layer>
The pressure-sensitive adhesive layer of this pressure-sensitive adhesive sheet laminate can function as a double-sided pressure-sensitive adhesive sheet when the covering portion I and the covering portion II are peeled off, and has a hot melt property that softens or melts when heated. That's fine.

The pressure-sensitive adhesive sheet laminate is usually heat-molded at 70 to 180 ° C. and then cooled to 30 to 50 ° C. to complete the molding. For example, when heat forming of the present pressure-sensitive adhesive sheet laminate is started at 100 ° C. and heat forming is terminated at 30 ° C., the loss tangent tan δ (SA) at the heat forming start temperature of 100 ° C. is 1.0. The above is preferable, and the loss tangent tan δ (SB) at 30 ° C., which is the heat forming end temperature, is preferably less than 1.0.
When the loss tangent tan δ (SA) at the heat forming start temperature is 1.0 or more, it becomes easy to form an uneven shape on the surface of the adhesive material layer.
In addition, if the loss tangent tan δ (SB) at the heat forming end temperature of the adhesive layer is less than 1.0, the sheet shape can be maintained in a normal state, so that the uneven shape coincides with the uneven portion on the adherend surface. Can be maintained with high accuracy on the surface of the adhesive layer.
Here, the loss tangent tan δ means the ratio (G ″ / G ′) between the loss elastic modulus G ″ and the storage elastic modulus G ′.
In general, a polymer material has both a viscous property and an elastic property, and the loss tangent tan δ is 1.0 or more, and the viscosity value becomes stronger as the value increases. On the other hand, the elastic property becomes stronger as the loss tangent tan δ is less than 1.0 and the value is further reduced. For this reason, by controlling the loss tangent tan δ at different temperatures of the adhesive layer, it becomes possible to have both formability and shape retention.

From this point of view, the loss tangent tan δ (SA) at the thermoforming start temperature of the pressure-sensitive adhesive layer is preferably 1.0 or more, particularly 1.5 or more and 30 or less, and more preferably 3.0 or more and 20 or less. Is preferred.
On the other hand, the loss tangent tan δ (SB) at the heat forming end temperature of the pressure-sensitive adhesive layer is preferably less than 1.0, particularly 0.01 or more and 0.9 or less, and more preferably 0.1 or more and 0.8 or less. Is preferred.

  Here, the loss tangent tan δ (SA) at the thermoforming start temperature of the adhesive material layer and the loss tangent tan δ (SB) at the thermoforming end temperature are the components, gel fraction, and weight average molecular weight of the composition constituting the adhesive material layer. It is possible to adjust to the above range by adjusting etc.

Furthermore, it is preferable that the storage elastic modulus G ′ (SA) at the thermoforming start temperature of the pressure-sensitive adhesive layer is less than 1.0 × 10 ⁴ Pa. Moreover, it is preferable that the storage elastic modulus G '(SB) in the thermoforming end temperature of the said adhesive material layer is 1.0 * 10 < ⁴ > Pa or more.
If the storage elastic modulus G ′ (SA) at the heat forming start temperature of the pressure-sensitive adhesive layer is less than 1.0 × 10 ⁴ Pa, it is preferable because sufficient moldability can be obtained. If the storage elastic modulus G ′ (SB) is 1.0 × 10 ⁴ Pa or more, it is preferable from the viewpoint of shape stability after molding.

From this point of view, the storage elastic modulus G ′ (SA) at the thermoforming start temperature of the pressure-sensitive adhesive layer is preferably less than 1.0 × 10 ⁴ Pa, among which 5.0 × 10 ¹ Pa or more or 5.0 ×. More preferably, it is 10 ³ Pa or less, and more preferably 1.0 × 10 ² Pa or more or 1.0 × 10 ³ Pa or less.
From this point of view, the storage elastic modulus G ′ (SB) at the end temperature of the pressure-sensitive adhesive layer is preferably 1.0 × 10 ⁴ Pa or more, and more preferably 2.0 × 10 ⁴ Pa or more. It is more preferably 0 × 10 ⁷ Pa or less, and more preferably 5.0 × 10 ⁴ Pa or more or 1.0 × 10 ⁶ Pa or less.

  Here, the storage elastic modulus G ′ (SA) at the thermoforming start temperature of the pressure-sensitive adhesive layer and the storage elastic modulus G ′ (SB) at the thermoforming end temperature of the pressure-sensitive adhesive layer are components of the composition constituting the pressure-sensitive adhesive layer. And the gel fraction, weight average molecular weight and the like can be adjusted to the above ranges.

The temperature at which the loss tangent tan δ of the adhesive layer is 1.0 is preferably 50 to 150 ° C., more preferably 50 ° C. or more and 130 ° C. or less, and more preferably 50 ° C. or more and 110 ° C. or less. .
If the temperature at which the loss tangent tan δ of the pressure-sensitive adhesive layer is 1.0 is 50 to 150 ° C., the pressure-sensitive adhesive sheet laminate can be molded by heating to 50 to 150 ° C.

The glass transition temperature (Tg) of the base resin of the adhesive layer is preferably −50 to 40 ° C., more preferably −30 ° C. or more or 25 ° C. or less, and particularly preferably −10 ° C. or more or 20 ° C. or less. Further preferred. Here, the measurement of the glass transition temperature refers to the midpoint between the inflection points of the baseline shift when the temperature is increased at a rate of 3 ° C./min using a differential scanning calorimeter (DSC).
If the glass transition temperature (Tg) of the base resin of the pressure-sensitive adhesive layer is within the above range, the pressure-sensitive adhesive layer can be given adhesiveness, and the temperature at which the loss tangent tan δ of the pressure-sensitive adhesive layer becomes 1.0 is set. It is possible to adjust to 50 to 150 ° C.

As the material of the adhesive layer, a conventionally known adhesive sheet can be used as long as it can be adjusted to a predetermined viscoelastic behavior.
For example, 1) a (meth) acrylic acid ester-based polymer (including a copolymer, hereinafter referred to as “acrylic ester-based (co) polymer”) is used as a base resin, and a crosslinking monomer is necessary for this. Depending on the pressure-sensitive adhesive sheet formed by blending a crosslinking initiator or a reaction catalyst,
2) A pressure-sensitive adhesive sheet formed by using a butadiene or isoprene-based copolymer as a base resin, blending a crosslinking monomer, a crosslinking initiator or a reaction catalyst as necessary, and causing a crosslinking reaction;
3) A pressure-sensitive adhesive sheet formed by crosslinking reaction by using a silicone polymer as a base resin, blending a crosslinking monomer, a crosslinking initiator or a reaction catalyst if necessary, and the like,
4) A polyurethane-based pressure-sensitive adhesive sheet using a polyurethane-based polymer as a base resin can be used.

The physical properties of the adhesive layer itself are not an essential problem in the present invention, except for the viscoelastic properties and thermal properties described above. However, from the viewpoints of tackiness, transparency, weather resistance, and the like, those using the acrylate ester (co) polymer of 1) as a base resin are preferable.
When performance such as electrical characteristics and low refractive index is required, those based on the butadiene or isoprene-based copolymer of 2) above are preferable.
When performances such as heat resistance and rubber elasticity in a wide temperature range are required, those using the silicone copolymer of 3) as a base resin are preferable.
When performance such as removability is required, those using the polyurethane polymer of 4) as a base resin are preferable.

As an example of the adhesive material layer, it was formed from a resin composition containing a (meth) acrylic copolymer (a) as a base resin, a crosslinking agent (b), and a photopolymerization initiator (c). An adhesive sheet can be illustrated.
In this case, it is necessary to satisfy the viscoelastic characteristics in an uncrosslinked state, that is, a state before photopolymerization. From this viewpoint, it is preferable that the gel fraction of the adhesive layer is 40% or less.

If the gel fraction of the pressure-sensitive adhesive layer is 40% or less, the bonding between the molecular chains constituting the pressure-sensitive adhesive layer is suppressed to an appropriate range, so that it has an appropriate fluidity when molded into a shaped pressure-sensitive adhesive sheet laminate. Can be provided.
From this viewpoint, the gel fraction of the pressure-sensitive adhesive layer is preferably 40% or less, more preferably 20% or less, and particularly preferably 10% or less. In addition, the minimum of the gel fraction of an adhesive material layer is not limited, 0% may be sufficient.
The gel fraction of the pressure-sensitive adhesive layer is a resin composition containing a (meth) acrylic copolymer (a), a crosslinking agent (b), and a photopolymerization initiator (c) as a base resin. The same applies to the case where other resin composition is used as the adhesive layer.

((Meth) acrylic copolymer (a))
The (meth) acrylic copolymer (a) has properties such as a glass transition temperature (Tg) as appropriate depending on the types and composition ratios of the acrylic and methacrylic monomers used for polymerizing the (meth) acrylic copolymer (a). It is possible to adjust.

  Examples of the acrylic monomer and methacrylic monomer used for polymerizing the acrylate polymer include 2-ethylhexyl acrylate, n-octyl acrylate, n-butyl acrylate, ethyl acrylate, methyl methacrylate, and the like. Vinyl acetate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, fluorine acrylate, silicone acrylate, etc., which are copolymerized with a hydrophilic group or an organic functional group, can also be used.

Among the acrylic ester polymers, (meth) acrylic acid alkyl ester copolymers are particularly preferable.
The (meth) acrylate used for forming the (meth) acrylic acid alkyl ester copolymer, that is, as the alkyl acrylate or alkyl methacrylate component, the alkyl group is n-octyl, isooctyl, 2-ethylhexyl, n-butyl, One of alkyl acrylate or alkyl methacrylate which is any one of isobutyl, methyl, ethyl and isopropyl, or a mixture of two or more selected from these is preferable.

As other components, an acrylate or methacrylate having an organic functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group may be copolymerized. Specifically, a monomer component obtained by appropriately and selectively combining the alkyl (meth) acrylate component and the (meth) acrylate component having an organic functional group as a starting material is subjected to heat polymerization to form a (meth) acrylate ester copolymer. A polymer polymer can be obtained.
Among them, preferably, an alkyl acrylate such as iso-octyl acrylate, n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture of two or more selected from these, or iso-octyl acrylate, Examples thereof include those obtained by copolymerizing at least one kind of n-octyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like with acrylic acid.

  As the polymerization treatment using these monomers, known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like can be employed. In this case, a thermal polymerization initiator or photopolymerization is used according to the polymerization method. An acrylic ester copolymer can be obtained by using a polymerization initiator such as an initiator.

(Acrylic copolymer (A1))
As an example of a preferable base polymer of the adhesive material layer, there can be mentioned a (meth) acrylic copolymer (A1) composed of a graft copolymer having a macromonomer as a branch component.

If the pressure-sensitive adhesive layer is composed of the acrylic copolymer (A1) as a base resin, the pressure-sensitive adhesive layer can exhibit self-adhesion while maintaining a sheet shape at room temperature, and when heated in an uncrosslinked state It has a hot melt property that melts or flows, and can be photocured, and after photocuring, it exhibits excellent cohesive force and can be bonded.
Therefore, if the acrylic copolymer (A1) is used as the base polymer of the adhesive material layer, even in an uncrosslinked state, it exhibits adhesiveness at room temperature (20 ° C.) and is more preferably 50 to 100 ° C. Can be softened or fluidized when heated to a temperature of 60 ° C. or higher or 90 ° C. or lower.

The glass transition temperature of the copolymer constituting the trunk component of the acrylic copolymer (A1) is preferably −70 to 0 ° C.
At this time, the glass transition temperature of the copolymer component constituting the trunk component refers to the glass transition temperature of a polymer obtained by copolymerizing only the monomer component composing the trunk component of the acrylic copolymer (A1). . Specifically, it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
In addition, the calculation formula of Fox is a calculation value calculated | required by the following formula | equation, Polymer handbook [Polymer HandBook, J.M. Brandrup, Interscience, 1989].
1 / (273 + Tg) = Σ (Wi / (273 + Tgi))
[Wherein Wi represents the weight fraction of monomer i, and Tgi represents Tg (° C.) of the homopolymer of monomer i. ]

The glass transition temperature of the copolymer component constituting the backbone component of the acrylic copolymer (A1) is the flexibility of the adhesive layer at room temperature, the wettability of the adhesive layer to the adherend, In order to affect the adhesiveness, the glass transition temperature is preferably −70 ° C. to 0 ° C., particularly −65 ° C. in order for the pressure-sensitive adhesive layer to obtain appropriate adhesiveness (tackiness) at room temperature. Above, or −5 ° C. or less, and particularly preferably −60 ° C. or more or −10 ° C. or less.
However, even if the glass transition temperature of the copolymer component is the same temperature, the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.

Examples of the (meth) acrylic acid ester monomer contained in the main component of the acrylic copolymer (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meta Acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl ( (Meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane acrylate, p-cumylphenol EO-modified (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, etc. . These include hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate having a hydrophilic group or an organic functional group, ) Acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalate Acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid Carboxyl group-containing monomers such as maleic acid, itaconic acid, monomethyl maleate and monomethyl itaconic acid, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate , Epoxy group-containing monomers such as (meth) acrylic acid 3,4-epoxybutyl, amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, (meth) Acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, maleimide, etc. Monomers containing amide group, vinyl pyrrolidone, vinyl pyridine, can also be used heterocyclic basic monomers such as vinyl carbazole.
Also, styrene, t-butylstyrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl, which can be copolymerized with the acrylic monomer or methacrylic monomer. Various vinyl monomers such as vinyl monomers can also be used as appropriate.

Moreover, it is preferable that the trunk component of the acrylic copolymer (A1) contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units.
If the trunk component of the acrylic copolymer (A1) is composed only of a hydrophobic monomer, a tendency to wet-heat whitening is recognized. Therefore, it is preferable to introduce a hydrophilic monomer into the trunk component to prevent wet-heat whitening. .

  Specifically, as the main component of the acrylic copolymer (A1), a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the end of the macromonomer are included. The copolymer component formed by random copolymerization can be mentioned.

Here, examples of the hydrophobic (meth) acrylate monomer include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) ) Acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meta) ) Acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate , Lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyloxyethyl Examples thereof include (meth) acrylate and methyl methacrylate.
Examples of the hydrophobic vinyl monomer include vinyl acetate, styrene, t-butyl styrene, α-methyl styrene, vinyl toluene, and alkyl vinyl monomers.

  Examples of the hydrophilic (meth) acrylate monomer include methyl acrylate, (meth) acrylic acid, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) ) Acrylate, hydroxyl-containing (meth) acrylate such as glycerol (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- ( TA) carboxyl group-containing monomers such as acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate, maleic anhydride, anhydrous Acid anhydride group-containing monomer such as itaconic acid, epoxy group-containing monomer such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate Examples thereof include alkoxy polyalkylene glycol (meth) acrylates such as N, N-dimethylacrylamide, hydroxyethylacrylamide and the like.

The acrylic copolymer (A1) preferably contains a macromonomer-derived repeating unit by introducing a macromonomer as a branch component of the graft copolymer.
The macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.

The glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (A1).
Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the adhesive layer 2, the glass transition temperature (Tg) of the macromonomer is 30 ° C to 120 ° C. Among them, it is preferable to be 40 ° C or higher or 110 ° C or lower, and it is more preferable to be 50 ° C or higher or 100 ° C or lower.
With such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and to adjust so as to hot-melt near 80 ° C.
The glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC).

Further, at room temperature, the branch components are attracted to each other and can maintain a state where they are physically cross-linked as a pressure-sensitive adhesive composition, and the physical cross-linking is released by heating to an appropriate temperature. In order to obtain fluidity, it is also preferable to adjust the molecular weight and content of the macromonomer.
From such a viewpoint, the macromonomer is preferably contained in the acrylic copolymer (A1) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or more and 25% by mass or less, and more preferably 8% by mass. It is preferable that the amount is 20% by mass or more.
The number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
As the macromonomer, a generally produced one (for example, a macromonomer manufactured by Toa Gosei Co., Ltd.) can be appropriately used.

The high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
Examples of the high molecular weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) ) Acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl ( (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) ) Acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane acrylate, p-cumylphenol EO modified (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylic acid, (Meth) acrylate monomers such as lysidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, alkoxyalkyl (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, , Styrene, t-butyl styrene, α-methyl styrene, vinyl toluene, alkyl vinyl monomer, vinyl acetate, alkyl vinyl ether, hydroxyalkyl vinyl ether, and other various vinyl monomers. These may be used alone or in combination of two or more. can do.

  Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.

(Crosslinking agent (b))
As the crosslinking agent (b), a crosslinking monomer used when the acrylic ester polymer is crosslinked can be used. For example, at least one crosslinkable functional group selected from (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, and amide group The crosslinking agent which has can be mentioned, You may use 1 type or in combination of 2 or more types.
The crosslinkable functional group may be protected with a deprotectable protecting group.

  Above all, a polyfunctional organic function having two or more organic functional groups such as a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, an isocyanate group, an epoxy group, a melamine group, a glycol group, a siloxane group or an amino group. An organometallic compound having a metal complex such as a base resin, zinc, aluminum, sodium, zirconium, or calcium can be preferably used.

  Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polyalkoxydi (meth) Acrylate, bisphenol F polyalkoxy di (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ε-caprolactone modified tris 2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propoxy Pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Di (meta) of ε-caprolactone adducts of acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxypentylglycol dipentaglycol di (meth) acrylate, hydroxybivalic acid neopenglycol ) In addition to UV-curable polyfunctional monomers such as acrylate, trimethylolpropane tri (meth) acrylate, alkoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, polyester (meth) acrylate, Polyfunctional acrylic oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyether (meth) acrylate can be exemplified.

Among the above-described polyfunctional (meth) acrylate monomers, polar functional groups such as a hydroxyl group, a carboxyl group, and an amide group from the viewpoint of improving the adhesion to the adherend and the effect of suppressing wet heat whitening. Polyfunctional monomers or oligomers containing are preferred. Among these, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group or an amide group.
From the viewpoint of preventing wet heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a trunk component of the (meth) acrylate copolymer, for example, a graft copolymer, Furthermore, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group as a crosslinking agent.
Moreover, in order to adjust effects, such as adhesiveness, heat-and-moisture resistance, and heat resistance, you may further add monofunctional or polyfunctional (meth) acrylic acid ester which reacts with a crosslinking agent.

  The content of the crosslinking agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer, from the viewpoint of balancing the flexibility and cohesive force of the pressure-sensitive adhesive composition. In particular, the ratio is preferably 0.5 parts by mass or more and 15 parts by mass or less, and particularly preferably 1 part by mass or more or 13 parts by mass or less.

(Photopolymerization initiator (c))
When crosslinking the acrylic ester polymer, a crosslinking initiator (peroxidation initiator, photopolymerization initiator) and reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.) are appropriately used. It is effective when added.

In the case of UV irradiation crosslinking, it is preferable to blend a photopolymerization initiator (c).
The photopolymerization initiator (c) is roughly classified into two types depending on the radical generation mechanism. The photopolymerization initiator is capable of generating a radical by cleaving the single bond of the photopolymerization initiator itself, and photoexcitation. In general, the initiator and the hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
Among these, the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, when the intramolecular cleavage type is used as a photopolymerization initiator having an absorption wavelength in the visible light region, light-reactive light is obtained after the pressure-sensitive adhesive sheet is cross-linked by light irradiation as compared with the case of using a hydrogen abstraction type. A polymerizable initiator is preferable because it remains as an unreacted residue in the pressure-sensitive adhesive composition and is unlikely to cause an unexpected change with time or promotion of crosslinking. Further, the coloring specific to the photopolymerizable initiator is also preferable because it becomes a reaction decomposition product, so that absorption in the visible light region is eliminated and a color to be erased can be appropriately selected.
On the other hand, a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. Damage to the body can be reduced.

  Examples of the cleavage type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1. -One, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy- 2-methyl-propionyl) benzyl} phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxy Methyl lickate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2- (dimethylamino) -2 -[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, and their derivatives Can be mentioned.

Among these, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine is a cleavage-type photopolymerization initiator, and becomes a degradation product after the reaction and discolors. Acylphosphine oxide photoinitiators such as fin oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide are preferred.
Furthermore, from the compatibility with an acrylic copolymer comprising a graft copolymer having a macromonomer as a branch component, 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator, It is preferable to use 6-trimethylbenzoyl) ethoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,4,4-trimethylpentylphosphine oxide, and the like.

The content of the photopolymerization initiator is not particularly limited. For example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic copolymer, particularly 0.2 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight. It is particularly preferable to include them in proportions. However, this range may be exceeded in balance with other elements.
A photoinitiator can be used 1 type or in combination of 2 or more types.

  In addition to the above components, pigments such as pigments and dyes having near-infrared absorption characteristics, tackifiers, antioxidants, antioxidants, hygroscopic agents, ultraviolet absorbers, silane coupling agents, natural products, Various additives such as synthetic resins, glass fibers and glass beads can be appropriately blended.

(Layer structure and thickness of adhesive layer)
The adhesive material layer may be a single layer or a plurality of layers such as two layers or three layers.
The pressure-sensitive adhesive layer may have a structure in which a base layer (non-sticky layer) is provided as a core layer, and layers made of a pressure-sensitive adhesive are laminated on both sides of the base layer. . In such a configuration, the base material layer as the core layer preferably has a material and characteristics such that the pressure-sensitive adhesive sheet laminate can be thermoformed. Further, the adhesive layer excluding the base material layer has the above-described characteristics with respect to loss tangent tan δ (SA), loss tangent tan δ (SB), storage elastic modulus G ′ (SA), and storage elastic modulus G ′ (SB). It is preferable.

The thickness of the adhesive layer is not particularly limited. Among these, a range of 20 μm to 500 μm is preferable. If it is this range, if it is a thin adhesive material layer like thickness 20 micrometers, the adhesive sheet excellent in the printing level | step difference followable | trackability can be provided. Moreover, in the thick adhesive material layer having a thickness of 500 μm, it is possible to suppress the overflow of the adhesive material at the time of pasting because the portion corresponding to the printing step is shaped in advance.
Accordingly, the thickness of the pressure-sensitive adhesive layer is preferably 20 μm to 500 μm, more preferably 30 μm or more and 300 μm or less, and particularly preferably 50 μm or more or 200 μm or less.

<Coating part I>
As shown in FIG. 1, the pressure-sensitive adhesive sheet laminate includes a covering portion I that is detachably laminated on one side of the pressure-sensitive adhesive layer, for example, on the side that forms irregularities on the surface.

The pressure-sensitive adhesive sheet laminate is usually heat-molded at 70 to 180 ° C. and then cooled to 30 to 50 ° C. to complete the molding. For example, when heat molding of the pressure-sensitive adhesive sheet laminate is started at 100 ° C. and the heat molding is finished at 30 ° C., the storage elastic modulus E ′ (MA) at 100 ° C., which is the heat molding start temperature of the covering portion I, is 1. It is preferable that it is 0 * 10 < ⁶ > -2.0 * 10 < ⁹ > Pa.
If the storage elastic modulus E ′ (MA) at the thermoforming start temperature is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, the covering portion I is in a temperature range where the pressure-sensitive adhesive composition is plasticized or flows. In addition to being able to be deformed by following the uneven shape sufficiently, it is possible to form the desired uneven shape on the surface of the adhesive layer pressed by the covering portion I at the time of molding with high accuracy, for example, so that the corners are not rounded. it can.

  Conventionally, a high storage elastic modulus, in other words, a “hard” material has been frequently used as a release film laminated on an adhesive sheet. This is because the properties required for the release film were mainly the protection of the adhesive layer and the release property. However, according to the study by the present inventors, when a new problem of thermoformability is required in a new application of thermoforming in a state where a release film is laminated on an adhesive sheet, a conventional release is required. It has been found that the above-mentioned physical properties provided in the mold film cannot be achieved. For this reason, as a result of scrutinizing the phenomena occurring at the time of thermoforming, the properties of the adhesive layer, etc., it is a new problem of thermoformability that has different characteristics from the release films that have been generally used so far It has been found that it is advantageous for solving the problem. In particular, it has been found that the above problem can be solved by controlling the storage elastic modulus at a specific temperature within a specific range.

From this point of view, the storage elastic modulus E ′ (MA) at the heat forming start temperature of the covering portion I is preferably 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and more preferably 5.0 × 10 ⁶ Pa. Above or 1.0 × 10 ⁹ Pa or less, more preferably 1.0 × 10 ⁷ Pa or more or 5.0 × 10 ⁸ Pa or less.

Further, the storage elastic modulus E in the heating forming finishing temperature of the coating portion I '(MB) is preferably a ^{5.0 × 10 7 ~1.0 × 10 10} Pa.
If the storage elastic modulus E ′ (MB) at the heat forming end temperature of the covering portion I is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa, shape retention can be maintained in a normal state. For example, not only is it easy to peel off but is not too hard, it is possible to suppress unnecessary undesired unevenness on the adhesive layer.
From this point of view, the storage elastic modulus E ′ (MB) at the heat forming end temperature of the covering portion I is preferably 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa, and more preferably 1.0 × 10 ⁸ Pa. Above or 8.0 × 10 ⁹ Pa or less, more preferably 1.0 × 10 ⁹ Pa or more or 5.0 × 10 ⁹ Pa or less.

  In order to adjust the storage elastic modulus E ′ of the covering portion I as described above, for example, the conditions of the material of the covering portion I such as the type of the base resin, the copolymer resin component, the weight average molecular weight, the glass transition temperature, and the crystallinity are set. While adjusting, it can adjust by adjusting manufacturing conditions, such as extending | stretching conditions, the presence or absence of extending | stretching, a molding condition, and extending. However, it is not limited to these methods.

Further, the storage elastic modulus E ′ (MA) at the heat forming start temperature of the covering portion I and the storage elastic modulus E ′ (MB) at the heat forming end temperature of the covering portion I satisfy the following relational expression (1). Is preferred.
(1) ··· E '(MB) / E' (MA) ≥3.0

It is sufficient if the storage elastic modulus E ′ (MA) at the heat forming start temperature of the covering portion I and the storage elastic modulus E ′ (MB) at the heat forming end temperature of the covering portion I satisfy the relational expression (1). This is because moldability is obtained.
From this point of view, it is preferable that E ′ (MB) / E ′ (MA) ≧ 3.0, among which 30 ≧ E ′ (MB) / E ′ (MA) or E ′ (MB) / E ′ (MA ) ≧ 3.0, more preferably 10 ≧ E ′ (MB) / E ′ (MA) or E ′ (MB) / E ′ (MA) ≧ 5.0.

  In order to adjust E ′ (MB) and E ′ (MA) to have the above relationship, for example, the type of base resin, copolymer resin component, weight average molecular weight, glass transition temperature, crystallinity, etc. While adjusting the conditions of the material, it can be adjusted by adjusting the presence / absence of stretching, molding conditions, and in the case of stretching, production conditions such as stretching conditions. However, it is not limited to these methods.

Furthermore, the storage elastic modulus G ′ (SA) at the thermoforming start temperature of the pressure-sensitive adhesive layer and the storage elastic modulus E ′ (MA) at the thermoforming start temperature of the covering portion I are expressed by the following relational expression (2). It is preferable to satisfy.
(2) .. E '(MA) / G' (SA) ≦ 1.0 × 10 ⁷

If the storage elastic modulus G ′ (SA) at the thermoforming start temperature of the pressure-sensitive adhesive layer and the storage elastic modulus E ′ (MA) at the thermoforming start temperature of the covering portion I satisfy the relational expression (2), It is further preferable because sufficient moldability can be obtained.
From this point of view, E ′ (MA) / G ′ (SA) is preferably 1.0 to 1.0 × 10 ⁷ , among which 1.0 × 10 ¹ or more or 5.0 × 10 ⁶ or less, Of these, 5.0 × 10 ¹ or more or 1.0 × 10 ⁶ or less is particularly preferable.

  In order to adjust E ′ (MA) and G ′ (SA) so as to satisfy the above relationship, the characteristics of the adhesive layer or the covering portion I may be adjusted. The characteristics of the pressure-sensitive adhesive layer can be achieved, for example, by adjusting the components, gel fraction, weight average molecular weight, and the like of the composition constituting the pressure-sensitive adhesive layer. In addition, as the characteristics of the covering portion I, for example, the conditions of the material of the covering portion I such as the type of the base resin, the copolymer resin component, the weight average molecular weight, the glass transition temperature, and the crystallinity are adjusted, whether or not there is stretching, molding In the case of stretching, it can be adjusted by adjusting the production conditions such as stretching conditions. However, it is not limited to these methods.

Further, it is preferable that the covering portion I has a peeling force F (C) of 0.2 N / cm or less when peeling the covering portion I from the adhesive layer in an atmosphere of 30 ° C.
When the peeling force F (C) is 0.2 N / cm or less, the covering portion I can be easily peeled from the adhesive material layer.
From such a viewpoint, the peeling force F (C) is preferably 0.2 N / cm or less, more preferably 0.01 N / cm or more or 0.15 N / cm or less, and more preferably 0.02 N / cm. / Cm or more or 0.1 N / cm or less is more preferable.

Furthermore, since the covering portion I generally undergoes a heating process during the molding process, it is preferable that the peeling force does not change even after heating. Specifically, the pressure-sensitive adhesive sheet laminate is heated at 100 ° C. for 5 minutes and then cooled to 30 ° C., and the peeling force F (D) when peeling the covering portion I from the pressure-sensitive adhesive layer in a 30 ° C. atmosphere is 0. It is preferable that it is 2 N / cm or less.
If the peel force F (D) obtained by heating the pressure-sensitive adhesive sheet laminate at 100 ° C. for 5 minutes and then cooling to 30 ° C. and measuring in an atmosphere at 30 ° C. is approximately the same as the peel force F (C) Even if the pressure-sensitive adhesive sheet laminate is thermoformed, the covering force I can be easily peeled off from the pressure-sensitive adhesive layer because the peeling force F (D) does not change.
From this viewpoint, the peeling force F (D) is preferably 0.2 N / cm or less, more preferably 0.01 N / cm or more or 0.15 N / cm or less, and more preferably 0.02 N / cm. / Cm or more or 0.1 N / cm or less is more preferable.

The covering portion I further preferably has an absolute value of a difference between the peeling force F (C) and the peeling force F (D) of 0.1 N / cm or less.
The pressure-sensitive adhesive sheet laminate is heated at 100 ° C. for 5 minutes and then cooled to 30 ° C., and the difference between the peel force F (D) obtained by measurement in an atmosphere at 30 ° C. and the peel force F (C) in a normal state If the absolute value is 0.1 N / cm or less, even if the pressure-sensitive adhesive sheet laminate is thermoformed, the peeling force F (D) does not change, so the covering portion I can be easily peeled from the pressure-sensitive adhesive layer. it can.
From this viewpoint, the absolute value of the difference between the peeling force F (C) and the peeling force F (D) is preferably 0.1 N / cm or less, more preferably 0.08 N / cm or less, and particularly 0.05 N / cm. More preferably, it is as follows.

  Note that the peeling force F (C) and the peeling force F (D) of the covering portion I can be prepared depending on the type of the release layer formed on one side of the covering portion I. However, it is not limited to this method.

  As a structural example of the coating | coated part I, the structural example provided with the coating | coated base material layer and the release layer can be mentioned. By laminating the release layer on one surface of the covering base material layer, the covering portion I can be configured to be easily peeled from the adhesive material layer.

  In this case, the covering base layer is, for example, a stretched or unstretched layer mainly composed of one type of resin or two or more types of resins selected from the group consisting of polyester, copolyester, polyolefin and copolyolefin. That is, it is preferably a single layer or a multilayer having a layer made of a stretched or non-stretched film containing these resins as a main component.

Among them, the covering base layer constituting the covering portion I is, for example, a copolymerized polyester, a polyolefin, or a stretched or non-stretched film containing a copolymerized polyolefin as a main component from the viewpoint of mechanical strength, chemical resistance, and the like. It is preferable that it is a single layer provided with the layer which consists of or multiple layers.
Specific examples of the copolymerized polyester include copolymerized polyethylene terephthalate obtained by arbitrarily copolymerizing isophthalic acid as a dicarboxylic acid, cyclohexanedimethanol, 1,4-butanediol, diethylene glycol, or the like as a diol. it can.
Specific examples of the polyolefin include an α-olefin homopolymer, and examples thereof include a propylene homopolymer and a homopolymer of 4-methylpentene-1.
Specific examples of the polyolefin copolymer include copolymers such as ethylene, propylene, other α-olefins and vinyl monomers.

The release layer is preferably a layer containing a modified polyolefin in addition to a release agent such as silicone.
Here, examples of the modified olefin constituting the release layer include resins mainly composed of an unsaturated carboxylic acid or an anhydride thereof, or a polyolefin modified with a silane coupling agent.

  Examples of the unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride or monoepoxy compounds of these derivatives and the acid. Ester compounds, polymers having a group capable of reacting with these acids in the molecule, and reaction products of the acids. These metal salts can also be used. Among these, maleic anhydride is more preferably used. Moreover, these copolymers can be used individually or in mixture of 2 or more types, respectively.

  In order to produce a modified polyolefin-based resin, for example, these modified monomers can be copolymerized in the stage of polymerizing the polymer in advance, or these modified monomers can be graft-copolymerized to the polymer once polymerized. Further, as the modified polyolefin resin, these modified monomers may be used alone or in combination, and the content thereof is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more. In the range of 5% by mass or less, preferably 4.5% by mass or less, more preferably 4.0% by mass or less is preferably used. Of these, those that have been graft-modified are preferably used.

  Preferable examples of the modified polyolefin resin include maleic anhydride modified polypropylene resin, maleic anhydride modified polyethylene resin, maleic anhydride ethylene-vinyl acetate copolymer and the like.

  From the viewpoint of moldability, the thickness of the covering portion I is preferably 10 μm to 500 μm, more preferably 20 μm or more and 300 μm or less, and particularly preferably 30 μm or more or 150 μm or less.

<Coating II>
As described above, this pressure-sensitive adhesive sheet laminate has a covering portion I laminated on the front and back sides of the pressure-sensitive adhesive layer so as to be peelable, and is peelable on the opposite side of the covering portion I, that is, on the other side of the pressure-sensitive adhesive layer It can be set as the structure which laminate | stacks the coating | coated part II. Thus, handling property can be improved by laminating | stacking the coating | coated part II on the front and back other side of an adhesive material layer so that peeling is possible.

  The covering part II is not particularly limited in its material and configuration as long as it is formed by being detachably laminated on the other side of the adhesive material layer.

The covering portion II may be, for example, the same laminated structure and material as the covering portion I, and may be the same thickness as the covering portion I or a different thickness.
If the covering part II is the same laminate structure and material as the covering part I, it is possible to prevent warping from occurring when the present adhesive sheet laminate is heated.

The covering portion II has the same configuration as the covering portion I, but has a storage elastic modulus E ′ (MA) at the heat forming start temperature, a storage elastic modulus E ′ (MB) at the heat forming end temperature, and a ratio thereof (E ′ (MB ) / E ′ (MA)), peel force F (C), peel force F (D), and the like may be different from those of the covering portion I.
Further, the covering portion II may have a laminated structure and material different from those of the covering portion I.
For the covering part II, for example, a generally used release film (also referred to as “release film”) can be used. Specifically, a material having a storage elastic modulus E ′ (MC) at a thermoforming start temperature of 2.0 × 10 ^{9 to} 1.0 × 10 ¹¹ Pa is exemplified. For example, biaxially stretched polyethylene terephthalate (PET) ) A film or the like can be used.

(Method for producing this pressure-sensitive adhesive sheet laminate)
As an example of the method for producing the present pressure-sensitive adhesive sheet laminate, there can be mentioned, for example, a method in which a pressure-sensitive adhesive composition is sandwiched between two covering parts I or II and a pressure-sensitive adhesive layer is formed using a laminator. Moreover, as another method, the method of apply | coating an adhesive composition to the coating | coated part I or II, and forming the adhesive material layer can be mentioned. However, it is not limited to this manufacturing method.
Examples of the method for applying the pressure-sensitive adhesive composition include conventionally known coating methods such as reverse roll coating, gravure coating, bar coating, and doctor blade coating.

[This shaped adhesive sheet laminate]
Next, the shaped pressure-sensitive adhesive sheet laminate 1 (referred to as “the present shaped pressure-sensitive adhesive sheet laminate 1”) as a suitable example of the shaped pressure-sensitive adhesive sheet laminate that can be produced by this production method will be described.

As shown in FIG. 3, the shaped adhesive sheet laminate 1 includes an adhesive material layer 2, a covering portion I that is detachably laminated on the front and back sides of the adhesive material layer 2, and the adhesive material layer 2. And the other side of the front and back of the cover part II that is laminated in a peelable manner,
The pressure-sensitive adhesive layer 2 includes a concave portion, a convex portion, or an uneven portion (referred to as “adhesive sheet surface uneven portion 2B”) on the front and back one side surface 2A, and the front and back other side surface 2C is a flat surface,
The covering portion I is in close contact with the front and back one side surface 2A of the pressure-sensitive adhesive sheet 2 and includes a concave portion, a convex portion, or an uneven portion (referred to as “covering portion surface uneven portion 3B”) on the front and back one side surface 3A. In addition, the sheet back surface 3C is provided with a convex portion, a concave portion or a convex concave portion (referred to as "protective sheet back surface convex concave portion 3D") that coincides with the adhesive sheet surface concave and convex portion 2B, in other words, is fitted.
The covering portion II may have a configuration including a flat surface along the front and back other surface 2C of the pressure-sensitive adhesive sheet 2.

  The front and back other surface 2C can be a flat surface as shown in FIG. 3, and the front and back other surface 2C can also be formed to have a concave portion, a convex portion, or an uneven portion. it can.

The present shaped pressure-sensitive adhesive sheet laminate 1 having such a structure is produced by, for example, as shown in FIG. 2, the present pressure-sensitive adhesive sheet laminate by press molding, vacuum forming, pressure forming, roll forming, or the like. It can manufacture by shape | molding an uneven | corrugated shape integrally with respect to this adhesive sheet laminated body by compression molding.
By manufacturing in this way, the pressure-sensitive adhesive sheet surface uneven portion 2B of the pressure-sensitive adhesive layer 2, the protective sheet surface uneven portion 3B and the protective sheet back surface concave / convex portion 3D of the covering portion I have unevenness corresponding to the same location, respectively. It can be.

The pressure-sensitive adhesive layer 2 can be used as a double-sided pressure-sensitive adhesive sheet for bonding together two image display device constituent members (each also referred to as “adhered body”) constituting the image display device, for example.
That is, the pressure-sensitive adhesive sheet surface uneven portion 2B in the pressure-sensitive adhesive layer 2 is a concave portion, a convex portion, or a concave-convex portion (“adhered surface uneven portion”) on the bonding surface (also referred to as “bonding surface”) of the adherend. So that they can be formed in the same contour shape. Therefore, the adhesive sheet surface uneven part 2B in the shaped adhesive sheet laminate 1 can be fitted to the adherend surface uneven part in the image display device constituting member as the adherend.

Here, as the image display device, for example, a smartphone or a tablet including a liquid crystal display device (LCD), an organic EL display device (OLED), electronic paper, a micro electro mechanical system (MEMS) display, a plasma display (PDP), and the like A terminal, a mobile phone, a television, a game machine, a personal computer, a car navigation system, an ATM, a fish finder, and the like can be given. However, it is not limited to these.
The image display device constituent member as the adherend is a member constituting these image display devices, and examples thereof include a surface protection panel, a touch panel, and an image display panel. 1 can be used for bonding any two adherends selected from, for example, a surface protection panel, a touch panel, and an image display panel. For example, it can be used to bond a surface protection panel and a touch panel, or a touch panel and an image display panel. However, the adherend is not limited to these.

<Application>
An example of usage of the shaped adhesive sheet laminate 1 will be described.
In recent years, as mobile phones, smartphones, tablet terminals, and the like are generalized, there are many cases in which an image display unit is damaged by a user accidentally dropping it. In particular, when the image display device is a touch panel system, not only the display becomes difficult to see due to breakage, but also the touch panel operation itself becomes impossible or causes a failure due to a physical failure or water intrusion. Therefore, there is a case where repair, that is, repair, in which only the image display unit is replaced, is performed.
In the repair of the image display device, the adhesive sheet is also used when a new image display unit is loaded. Usually, repair is often performed as a manual work by a repair worker, and skill of the repair worker is required. That is, if it is not an expert, when an image display part is loaded via an adhesive sheet, air will enter inside or an adhesive material will protrude.
On the other hand, if this shaped adhesive sheet laminate 1 is used, a highly accurate step shape or the like can be given in advance. For example, a step shape corresponding to the model of the image display device is given in advance to the adhesive material layer. By doing so, the repair work is greatly simplified and can be carried out without requiring the skill of a repair worker. Thus, the pressure-sensitive adhesive sheet laminate of the present invention can be usefully used for repairing image display devices.

<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” or “preferably Y”. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.

  In the present invention, the boundary between the sheet and the film is not clear, and it is not necessary to distinguish the two in terms of the wording in the present invention. Therefore, in the present invention, even when the term “film” is used, the term “sheet” is included. "Film" is also included.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.

<Measurement and evaluation method>
First, measurement methods and evaluation methods for various physical property values of samples obtained in Examples and Comparative Examples will be described.

(Elastic modulus of the coating)
The storage elastic modulus E ′ (MS) and E ′ (MF) of the covering portion I are cut into a length of 50 mm and a width of 4 mm, and between chucks using a dynamic viscoelastic device (ITA Measurement Control Co., Ltd. DVA-200). The distance was measured with a strain of 25 mm and 1%. The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the temperature increase rate was 3 ° C./min.
The value of the storage elastic modulus at each molding start temperature in Examples and Comparative Examples was E ′ (MS), and the value of the storage elastic modulus at each molding end temperature was E ′ (MF).

In Example 1, since the temperature at the start of molding is 100 ° C., the storage elastic modulus E ′ (MS) of Example 1 is the storage elastic modulus E ′ (MA) at 100 ° C.
Moreover, since the end-of-molding temperature was 30 ° C. for any of the examples and comparative examples, the E ′ (MF) for each of the examples and comparative examples was the storage elastic modulus E ′ (MB) at 30 ° C. ).

(Elastic modulus of adhesive layer)
The pressure-sensitive adhesive layers obtained in Examples and Comparative Examples were stacked to a thickness of 1 mm and measured using a rheometer (MARSII manufactured by Thermo Fisher Scientific). The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the temperature increase rate was 3 ° C./min.
In the obtained data, the value of storage elastic modulus at 100 ° C. is G ′ (SA), the value of loss elastic modulus is G ″ (SA), the value of storage elastic modulus at 30 ° C. is G ′ (SB), the loss The value of elastic modulus was G ″ (SB), and the value of G ″ / G ′ under each temperature condition was the loss tangent tan δ (SA, SB) of each adhesive material layer.

On the other hand, for the storage elastic moduli G ′ (SA) and G ′ (SB) of the adhesive material layer, the adhesive material layers obtained in Examples and Comparative Examples were stacked to a thickness of 1 mm, and a rheometer (thermo-fischer) was obtained. The measurement was performed using MARSII manufactured by Scientific. The measurement temperature range was −50 ° C. to 150 ° C., the frequency was 1 Hz, and the temperature increase rate was 3 ° C./min.
In the obtained data, the value of the storage elastic modulus at each molding start temperature in Examples and Comparative Examples is G ′ (SS), the value of the loss elastic modulus is G ″ (SS), and the temperature at each molding end temperature is The value of storage elastic modulus is G ′ (SF), the value of loss elastic modulus is G ″ (SF), and the value of G ″ / G ′ under each temperature condition is the loss tangent tan δ of each adhesive layer. (SS, SF).

(Gel fraction)
About the gel fraction of the adhesive material layer, about 0.05 g of each of the adhesive material layers obtained in Examples and Comparative Examples was sampled and formed into a bag shape with a SUS mesh (# 200) whose mass (X) was measured in advance. After wrapping and closing the mouth of the bag, the mass (Y) of the wrap is measured, immersed in 100 ml of ethyl acetate and stored in the dark at 23 ° C. for 24 hours, then the package is taken out and 4. It was heated for 5 hours to evaporate the attached ethyl acetate, the mass (Z) of the dried packet was measured, and the obtained mass was substituted into the following formula.
Gel fraction [%] = [(Z−X) / (Y−X)] × 100

(Formability)
The covering part I of the shaped pressure-sensitive adhesive sheet laminate formed with unevenness obtained in Examples and Comparative Examples was peeled off, and the heights of the concave part corresponding to the printing step and the convex part corresponding to the display surface were respectively determined. Measurements were made in a non-contact manner using a scanning white interference microscope.
Measure the height h of the convex part (edge part with the concave part) of the molded body with respect to the depth of the mold of 100 μm, and the transfer rate derived from the following calculation formula is 50% or more: ○, less than 50% Each was evaluated as x.
Transfer rate (%) = h (molded body height) / 100 (mold depth) × 100

(Peeling force)
The pressure-sensitive adhesive sheet laminates produced in Examples and Comparative Examples were cut into a length of 150 mm and a width of 50 mm, and the 180 ° peel test was performed on the interface between the covering portion I and the pressure-sensitive adhesive layer at a test speed of 300 mm / min.
The peel force in a 30 ° C. environment is F (C), and after heating at 100 ° C. for 5 minutes and then naturally cooling to 30 ° C., the peel force is F (D). Power.

<Coating part I>
As a covering part I of the pressure-sensitive adhesive sheet laminate in Examples and Comparative Examples, a release layer (thickness: 2 μm) made of a silicone compound is laminated on one side of a biaxially stretched isophthalic acid copolymerized PET film (thickness: 75 μm). The film formed was used. Each storage modulus value is shown in Table 1.

<Example 1>
(Production of double-sided PSA sheet)
As the (meth) acrylic copolymer (a), a polymethyl methacrylate macromonomer having a number average molecular weight of 2400 (Tg: 105 ° C.) 15 parts by mass (18 mol%) and butyl acrylate (Tg: −55 ° C.) 81 parts by mass 1 kg of an acrylic copolymer (a-1) (weight average molecular weight 230,000) obtained by random copolymerization of (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.), and a crosslinking agent As (b), glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (b-1) 90 g, and photopolymerization initiator (c) as 2,4,6-trimethylbenzophenone and 4-methylbenzophenone 15 g of a mixture (manufactured by Lanberti, product name: Ezacure TZT) (c-1) was uniformly mixed to prepare a resin composition 1 used for an adhesive layer. The obtained resin composition had a glass transition temperature of −5 ° C.

  The obtained resin composition 1 was sandwiched between two pieces of a PET film (Mitsubishi Resin Co., Ltd., product name: Diafoil MRV-V06, thickness: 100 μm) and a coating part I, and a laminator was used. The pressure-sensitive adhesive sheet laminate 1 was produced by shaping the resin composition 1 into a sheet shape so that the thickness was 100 μm. In addition, it arrange | positioned so that the mold release layer side of the coating | coated part I might contact | connect the resin composition 1. FIG.

The obtained pressure-sensitive adhesive sheet laminate 1 is thermoformed by the following process using a vacuum / pressure forming machine (manufactured by Daiichi Jitsugyo Co., Ltd., model FKS-0632-20) and a molding die, and is shaped into a pressure-sensitive adhesive sheet. Body 1 was produced.
As shown in FIG. 6, the mold for molding is a convex mold having a length of 270 mm, a width of 170 mm, and a thickness of 40 mm, and the upper and lower molds have a length of 270 mm and a width. The aluminum plate was 170 mm and 40 mm thick. As shown in FIG. 6, a convex portion having a length of 187 mm, a width of 125 mm, and a height of 1 mm is provided in the center on the molding surface of the convex mold, and the depth is 25 μm and 50 μm in the molding surface of the convex portion. , 75 μm and 100 μm, four rectangular recesses (89 mm long and 58 mm wide) in plan view were provided.

With the IR heater preheated to 400 degreeC, it heated and shape | molded until the surface of the coating part I of the adhesive sheet laminated body 1 became 100 degreeC. That is, in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 2.1 × 10 ⁸ Pa and the storage elastic modulus G ′ (SS) of the adhesive layer is 2.9 × 10 ² Pa, Using a molding die whose mold surface temperature was cooled to 30 ° C., press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, and the storage elastic modulus E ′ (MF) of the covering portion I was 2.8 × 10. ^The shaped pressure-sensitive adhesive sheet laminate 1 is ⁹ Pa, the mold is opened in a state where the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 6.1 × 10 ⁴ Pa, and the surface is unevenly shaped. Produced.

The ratio E ′ (MF) / E ′ (MS) of the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion I at the end of the forming. Was 13.3.
Further, the ratio E ′ (MF) / G ′ (SF) of the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. Was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 4.8, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Example 2>
The pressure-sensitive adhesive sheet laminate 1 used in Example 1 was heated and molded using an IR heater preheated to 400 ° C. until the surface of the covering portion I of the pressure-sensitive adhesive sheet laminate 2 reached 110 ° C. That is, in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 1.3 × 10 ⁸ Pa and the storage elastic modulus G ′ (SS) of the adhesive layer is 9.6 × 10 ¹ Pa, Using a molding die whose mold surface temperature was cooled to 30 ° C., press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, and the storage elastic modulus E ′ (MF) of the covering portion I was 2.8 × 10. ^The shaped pressure-sensitive adhesive sheet laminate 2 is ⁹ Pa, the mold is opened in a state where the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 6.1 × 10 ⁴ Pa, and the surface is unevenly shaped. Produced.

<Example 3>
The pressure-sensitive adhesive sheet laminate 1 used in Example 1 was heated and molded using an IR heater preheated to 400 ° C. until the surface of the covering portion I of the pressure-sensitive adhesive sheet laminate 3 reached 90 ° C. That is, in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 3.5 × 10 ⁸ Pa and the storage elastic modulus G ′ (SS) of the adhesive layer is 8.9 × 10 ² Pa, Using a molding die whose mold surface temperature was cooled to 30 ° C., press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, and the storage elastic modulus E ′ (MF) of the covering portion I was 2.8 × 10. ^The shaped pressure-sensitive adhesive sheet laminate 3 is ⁹ Pa, the mold is opened in a state where the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 6.1 × 10 ⁴ Pa, and the surface is unevenly shaped. Produced.

The ratio E ′ (MF) / E ′ (MS) of the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion I at the end of the forming. Was 8.0.
Further, the ratio E ′ (MF) / G ′ (SF) of the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. Was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 2.7, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Example 4>
The pressure-sensitive adhesive sheet laminate 1 used in Example 1 was heated and molded using an IR heater preheated to 400 ° C. until the surface of the covering portion I of the pressure-sensitive adhesive sheet laminate 4 reached 70 ° C. That is, in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 1.9 × 10 ⁹ Pa and the storage elastic modulus G ′ (SS) of the adhesive layer is 6.4 × 10 ³ Pa, Using a molding die whose mold surface temperature was cooled to 25 ° C., press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, and the storage elastic modulus E ′ (MF) of the covering portion I was 2.8 × 10. ^The shaped pressure-sensitive adhesive sheet laminate 4 is ⁹ Pa, the mold is opened in a state where the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 6.1 × 10 ⁴ Pa, and the surface is unevenly shaped. Produced.

The ratio E ′ (MF) / E ′ (MS) of the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion I at the end of the forming. Was 1.4.
Further, the ratio E ′ (MF) / G ′ (SF) of the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. Was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 1.4, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

<Comparative Example 1>
The pressure-sensitive adhesive sheet laminate 1 used in Example 1 was heated and molded using an IR heater preheated to 400 ° C. until the surface of the covering portion I of the pressure-sensitive adhesive sheet laminate 5 reached 60 ° C. That is, in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 2.4 × 10 ⁹ Pa and the storage elastic modulus G ′ (SS) of the adhesive layer is 1.3 × 10 ⁴ Pa, Using a molding die whose mold surface temperature was cooled to 25 ° C., press molding was performed for 5 seconds under the condition of a clamping pressure of 8 MPa, and the storage elastic modulus E ′ (MF) of the covering portion I was 2.8 × 10. ^The shaped pressure-sensitive adhesive sheet laminate 5 is ⁹ Pa, the mold is opened in a state where the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer is 6.1 × 10 ⁴ Pa, and the surface is unevenly shaped. Produced.

The ratio E ′ (MF) / E ′ (MS) of the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion I at the end of the forming. Was 1.2.
Further, the ratio E ′ (MF) / G ′ (SF) of the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. Was 4.6 × 10 ⁴ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 1.1, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

The ratio E ′ (MF) / E ′ (MS) of the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding to the storage elastic modulus E ′ (MF) of the covering portion I at the end of the forming. Was 8.0.
Further, the ratio E ′ (MF) / G ′ (SF) of the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding to the storage elastic modulus G ′ (SF) of the adhesive layer at the end of molding. Was 9.7 × 10 ³ .
Further, the loss tangent tan δ (SS) of the adhesive layer at the start of molding was 0.6, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding was 0.6.

  The evaluation results of the shaped pressure-sensitive adhesive sheet laminates 1 to 5 obtained in Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

From the results of Table 1, FIG. 4 and FIG. 5 and the test results conducted so far, as shown in Examples 1 to 3, the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding is 1. 0.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and the storage elastic modulus E ′ (MF) of the covering portion I at the end of molding is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa. It was confirmed that the uneven shape can be shaped with high accuracy in the adhesive material layer by performing the adjustment so as to be.
On the other hand, as shown in Comparative Example 1, when the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding is larger than 2.0 × 10 ⁹ Pa, it is sufficient for the adhesive layer even if thermoforming is performed. Unevenness could not be formed.
From the above, the storage elastic modulus E ′ (MS) of the covering portion I at the start of molding is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and the storage of the covering portion I at the end of molding is performed. By adjusting the elastic modulus E ′ (MF) to be 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa and performing molding, it is possible to obtain a shaped pressure-sensitive adhesive sheet that is formed with good unevenness. I understood that I could do it.

  More preferably, the loss tangent tan δ (SS) of the adhesive layer at the start of molding satisfies the condition of 1.0 or more, and the loss tangent tan δ (SF) of the adhesive layer at the end of molding is less than 1.0. It was also found that more accurate shaping can be achieved by performing molding while adjusting so as to satisfy the above.

  Therefore, by using the pressure-sensitive adhesive sheet laminate as described above, the unevenness corresponding to the printing steps of the image display device as the adherend is accurately shaped, so that there is no gap between the adherend and the printing. It is possible to confirm that a shaped pressure-sensitive adhesive sheet laminate for an image display device that can be satisfactorily bonded without causing the adhesive material to overflow even on an adherend having a narrow frame design can be manufactured. did it.

  Moreover, when it sees about peeling force, the heating-cooling conditions at the time of measuring peeling force F (D), ie, the conditions which carry out natural cooling to 30 degreeC after heating for 5 minutes at 100 degreeC manufacture a shaped adhesive sheet laminated body. This is a typical heating / cooling condition. In all of the above examples, the absolute value of the difference between the peeling force F (C) and the peeling force F (D) was 0.1 N / cm or less, so it was confirmed that the peeling force hardly changed before and after heating. It was done.

Furthermore, the pressure-sensitive adhesive sheet laminate is heated to start molding in a state where the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa. When the storage elastic modulus E ′ (MF) of the material is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa, the molding is finished to form a concavo-convex shape that matches the concavo-convex portion of the adherend surface. It was found that it can be formed on the surface of the layer with high accuracy.

Claims (11)

An adhesive material layer and a covering portion I that is detachably laminated on one surface of the adhesive material layer, and one surface of the adhesive material has a concave portion, a convex portion, or an uneven portion ("adhesive material layer surface uneven portion"). In the manufacturing method of a shaped pressure-sensitive adhesive sheet laminate having a configuration formed by
The pressure-sensitive adhesive layer is provided with an adhesive material layer and a covering portion I that is detachably laminated on one surface of the pressure-sensitive adhesive material layer, and the heated pressure-sensitive adhesive sheet laminate is formed and cooled to form pressure-sensitive adhesive. A manufacturing method for manufacturing a sheet laminate,
The pressure-sensitive adhesive sheet laminate is heated, and molding is started in a state where the storage elastic modulus E ′ (MS) of the covering part I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and the covering part I is stored. A method for producing a shaped pressure-sensitive adhesive sheet laminate, wherein the molding is terminated in a state where the elastic modulus E ′ (MF) is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa.   Heating the pressure-sensitive adhesive sheet laminate including the pressure-sensitive adhesive layer and the covering portion I laminated to be peelable on one surface of the pressure-sensitive adhesive layer, and using the cooled mold, the heated pressure-sensitive adhesive sheet laminate The method for producing a shaped pressure-sensitive adhesive sheet laminate according to claim 1, wherein the molding is performed. The storage elastic modulus E ′ (MS) of the covering portion I at the start of molding and the storage elastic modulus E ′ (MF) of the covering portion I at the end of forming satisfy the following relational expression (1): The manufacturing method of the shaped adhesive sheet laminated body of Claim 1 or 2 to do.
(1) E '(MF) / E' (MS) ≧ 1.3 By heating the pressure-sensitive adhesive sheet laminate, the storage elastic modulus E ′ (MS) of the covering portion I is 1.0 × 10 ^{6 to} 2.0 × 10 ⁹ Pa, and the storage elastic modulus G ′ of the pressure-sensitive adhesive layer is Molding is started in a state where (SS) is less than 1.0 × 10 ⁴ Pa,
The storage elastic modulus E ′ (MF) of the covering portion I is 5.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Pa, and the storage elastic modulus G ′ (SF) of the adhesive layer is 1.0 × 10 ^4. The method for producing a shaped pressure-sensitive adhesive sheet laminate according to any one of claims 1 to 3, wherein the molding is terminated in a state of Pa or higher. The storage elastic modulus E ′ (MF) of the covering portion I at the end of the molding and the storage elastic modulus G ′ (SF) of the pressure-sensitive adhesive layer at the end of the molding satisfy the following relational expression (2). The manufacturing method of the shaped adhesive sheet laminated body in any one of Claims 1-4.
(2) E ′ (MF) / G ′ (SF) ≦ 1.0 × 10 ⁷ The covering portion I includes a covering base material layer and a release layer,
The coating substrate layer is mainly composed of one type of resin or two or more types of resins selected from the group consisting of non-stretched polyester, stretched polyester, copolymerized polyester, unstretched polyolefin, stretched polyolefin and copolymerized polyolefin. It has a layer, The manufacturing method of the shaped adhesive sheet laminated body in any one of Claims 1-5 characterized by the above-mentioned.   The pressure-sensitive adhesive layer is formed from a resin composition containing a (meth) acrylic copolymer (a), a crosslinking agent (b), and a photopolymerization initiator (c). The manufacturing method of the shaped adhesive sheet laminated body in any one of claim | item 1 -6. In the shaped pressure-sensitive adhesive sheet laminate, the pressure-sensitive adhesive layer includes a concave portion, a convex portion, or a concave-convex portion (referred to as “pressure-sensitive adhesive layer surface concave-convex portion”) on the front and back side surfaces, and
The covering portion I is in close contact with the front and back side surfaces of the pressure-sensitive adhesive layer, and has a concave portion, a convex portion, or an uneven portion (referred to as a “cover portion surface uneven portion”) on the front and back side surface, It is provided with a convex portion or a concave portion or a convex concave portion (referred to as a “covered portion back surface convex concave portion”) corresponding to the surface irregularity portion of the covering portion on the front and back other surface opposite to the side. The manufacturing method of the shaped adhesive sheet laminated body in any one of Claims 1-7. The pressure-sensitive adhesive layer is a double-sided pressure-sensitive adhesive sheet for bonding two adherends,
The pressure-sensitive adhesive layer surface unevenness portion corresponds to a concave portion, a convex portion, or an uneven portion (referred to as an “adherent surface unevenness portion”) on the adherend surface of any one of the adherends. The manufacturing method of the shaped adhesive sheet laminated body of Claim 8.   The method for producing a shaped pressure-sensitive adhesive sheet laminate according to claim 9, wherein any one of the adherends is selected from the group consisting of a surface protection panel, a touch panel and an image display panel.   The pressure-sensitive adhesive sheet laminate is heated, and an uneven shape is formed on at least one surface of the pressure-sensitive adhesive sheet by press forming, vacuum forming, pressure forming or roll forming. A method for producing a shaped adhesive sheet laminate.

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