JPWO2015152365A1 - Adhesive sheet and method for producing adhesive sheet - Google Patents

Abstract

A release layer (R1) has a resin layer including a resin portion (X) and a particle portion (Y), and a substrate or a release material (R2), and at least the release material (R1) is provided on the side where the release material (R1) is provided. The surface (1) of the resin layer is a pressure-sensitive adhesive sheet, and the resin portion (X) on the surface (1) has an elastic modulus at 23 ° C. within a predetermined range, and the release material (R1) is removed. When removed, in a predetermined region arbitrarily selected on the surface (1) of the exposed resin layer, a recess having a maximum height difference of 100 nm or more and 95% or more having different shapes from each other ( Z1) appears in a plurality, and the maximum height of 0.5 μm or more is within a predetermined region arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided. Adhesive sheet having a plurality of recesses (Z2) having a difference and 95% or more having different shapes. To provide the door. The pressure-sensitive adhesive sheet has excellent air bleeding properties, and also has good blister resistance and pressure-sensitive adhesive properties.

Description

  The present invention relates to a pressure-sensitive adhesive sheet and a method for producing a pressure-sensitive adhesive sheet.

A general pressure-sensitive adhesive sheet is composed of a base material, a pressure-sensitive adhesive layer formed on the base material, and a release material provided on the pressure-sensitive adhesive layer as necessary. In the case where a material is provided, the release material is peeled off, and the pressure-sensitive adhesive layer is abutted against the adherend and attached.
By the way, for example, a pressure-sensitive adhesive sheet having a large application area used for identification / decoration, coating masking, surface protection of a metal plate, etc., is applied to an adherend with an adhesive layer and an adherend. There is a problem that air pockets are easily generated between them, and the portion becomes “bulging”, making it difficult to adhere the adhesive sheet to the adherend.

In order to solve such a problem, for example, in Patent Document 1, a release material having a fine emboss pattern is brought into contact with the surface of the pressure-sensitive adhesive layer, and a groove having a specific shape is formed on the surface of the pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet that is artificially arranged in a predetermined pattern is disclosed.
By using such an adhesive sheet, it is said that “air pockets” generated when sticking to an adherend can be released to the outside through a groove artificially formed on the surface of the adhesive layer. ing.

Special table 2001-507732 gazette

However, the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which grooves having a specific shape are arranged in a predetermined pattern, as described in Patent Document 1 or the like, is difficult to release air when the groove width is narrow, There is a problem that not only the surface substrate is recessed and the appearance is inferior, but also the adhesive strength is lowered.
In addition, since the adhesive sheet has the grooves arranged in a predetermined pattern, the adhesive strength of the place where the grooves are arranged is locally inferior, and when the adhesive sheet is attached to the adherend, the adhesive sheet does not peel off from the place. May occur.
On the other hand, when the pressure-sensitive adhesive sheet is peeled off after being adhered to the adherend, the pressure-sensitive adhesive properties of the pressure-sensitive adhesive sheet are locally different. Therefore, depending on the direction in which the pressure-sensitive adhesive sheet is peeled off, there is a possibility that adhesive residue may be generated on the adherend. For example, in the case of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which grooves are arranged in a lattice shape, adhesive residue may occur on the adherend when peeled in an oblique direction.
Further, when the punching process is performed on the pressure-sensitive adhesive sheet, the groove arrangement pattern and the punching pattern may overlap. In that case, there is a problem that the cutting depth varies, and the cutting cannot be appropriately formed in the adhesive sheet.

Moreover, generally, in order to make it easy to peel off the release material provided on the pressure-sensitive adhesive sheet, there is a case where a process (so-called back cracking process) is performed in which only the release material is cut and a trigger for peeling is provided. When performing the said process, after peeling off a peeling material from an adhesive sheet once and giving a cut | incision in a peeling material, it is common to laminate the peeling material and the adhesive layer of an adhesive sheet again.
However, since the embossed liner is used as the release material in the pressure-sensitive adhesive sheet described in Patent Document 1, it is difficult to follow the emboss pattern of the release material when laminating the release material and the adhesive layer again. It is necessary to prepare another release material that has not been subjected to.

Furthermore, in Patent Document 1, in order to form a fine structure in the pressure-sensitive adhesive layer, a method of laminating the pressure-sensitive adhesive layer and the base material after the pressure-sensitive adhesive is once applied to the emboss liner to form the pressure-sensitive adhesive layer ( The so-called transfer coating method is employed. However, when a base material having a low polarity surface such as a polyolefin base material is used as the base material, sufficient adhesion cannot be obtained at the interface between the base material and the pressure-sensitive adhesive layer.
In addition, unlike a release material made of paper, a release material made of a resin film makes it difficult to form a fine emboss pattern on the adhesive layer.
In addition, since the pressure-sensitive adhesive sheet described in Patent Document 1 is inferior in blister resistance, there is a problem that blisters are likely to occur when used at high temperatures.

  The present invention provides a pressure-sensitive adhesive sheet that has excellent air bleedability capable of easily removing air pockets that may be generated when affixed to an adherend, and also has good blister resistance and adhesive properties. For the purpose.

  The present inventor has a resin layer including a resin portion containing a resin as a main component and a particle portion made of fine particles, and in each of predetermined regions on two surfaces of the resin layer, A pressure-sensitive adhesive sheet having a plurality of concave portions having a maximum height difference of a specific value or more and having a plurality of concave portions having a predetermined ratio or more different from each other has been found to solve the above-mentioned problems. Completed.

That is, the present invention provides the following [1] to [21].
[1] On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a shape, and 95% or more of the plurality of recesses (Z1) appearing in the region (P1) have shapes different from each other,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more There are a plurality of recesses (Z2) having a maximum height difference, and 95% or more of the plurality of recesses (Z2) present in the region (P2) have shapes different from each other (hereinafter referred to as “first” Also called "adhesive sheet".
[2] A resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on the release material (R1), and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1), and 95% or more of the plurality of recesses (Z1) present in the region (P1) have shapes different from each other,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more There are a plurality of recesses (Z2) having a maximum height difference, and 95% or more of the plurality of recesses (Z2) present in the region (P2) have shapes different from each other (hereinafter referred to as “second” Also called "adhesive sheet".
[3] The pressure-sensitive adhesive sheet according to the above [1], wherein the shape of the sticking surface on the exposed surface (1) of the resin layer is indefinite.
[4] When the release material (R1) is removed and the surface (1) of the exposed resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted, the surface (1) The pressure-sensitive adhesive sheet according to any one of [1] to [3] above, wherein an area ratio of a pasted portion with the smooth surface of the translucent adherend is 60 to 99.999%.
[5] When the release material (R1) is removed and the surface (1) of the exposed resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted, the surface (1) The pressure-sensitive adhesive sheet according to any one of the above [1] to [4], wherein the shape of the pasted portion with the smooth surface of the translucent adherend is indefinite.
[6] The pressure-sensitive adhesive sheet according to any one of [1] to [5], wherein the plurality of recesses (Z1) appear or exist irregularly on the surface (1) of the resin layer.
[7] One or more of the recesses (Z1) appearing or existing in the region (P1) on the surface (1) extend to any side of a square with a side of 5 mm, which is the boundary line of the region (P1). The adhesive sheet according to any one of [1] to [6] above.
[8] One or more of the recesses (Z1) appearing or existing in the region (P1) on the surface (1) are surrounded by a square having a side of 5 mm adjacent to the region (P1). The pressure-sensitive adhesive sheet according to the above [7], which has a shape extending continuously into the region (P1 ′).
[9] Any of [1] to [8] above, wherein one or more recesses (Z2) are present in a region (Q2) surrounded by a square of 1 mm on an arbitrarily selected surface on the surface (2). The pressure-sensitive adhesive sheet according to claim 1.
[10] The pressure-sensitive adhesive sheet according to any one of [1] to [9], wherein the resin contained in the resin portion (X) includes a pressure-sensitive adhesive resin.
[11] The pressure-sensitive adhesive sheet according to any one of [1] to [10], wherein the resin contained in the resin portion (X) includes a resin having a functional group.
[12] The pressure-sensitive adhesive sheet according to [11], wherein the functional group is a carboxyl group.
[13] The pressure-sensitive adhesive sheet according to the above [11] or [12], wherein the resin portion (X) further contains one or more selected from a metal chelate crosslinking agent and an epoxy crosslinking agent.
[14] The pressure-sensitive adhesive sheet according to any one of [11] to [13], wherein the resin portion (X) includes both a metal chelate crosslinking agent and an epoxy crosslinking agent.
[15] The pressure-sensitive adhesive sheet according to any one of [1] to [14], wherein the fine particles are one or more selected from silica particles, metal oxide particles, and smectites.
[16] The adhesive according to any one of [1] to [15], wherein the surface (2) of the resin layer has adhesiveness, and a release material (R2) is laminated on the surface (2). Sheet.
[17] The pressure-sensitive adhesive sheet according to any one of [1] to [16], wherein a mass retention after heating the resin layer at 800 ° C. for 30 minutes is 3 to 90% by mass.
[18] Any one of the above-mentioned [1] to [17], wherein the surface of the release material (R1) in contact with the surface (1) of the resin layer is a release treatment surface on which no concavo-convex shape is formed. The pressure-sensitive adhesive sheet according to item.
[19] The pressure-sensitive adhesive sheet according to any one of [1] to [18], wherein the concave portion (Z2) is not formed by transferring an emboss pattern.
[20] The resin layer includes, from the release material (R1) side, a layer (X1) mainly including the resin portion (X), a layer (Y1) including 15% by mass or more of the particle portion (Y), and mainly a resin. The pressure-sensitive adhesive sheet according to any one of the above [1] to [19], which has a multilayer structure in which the layer (X2) including the part (X) is laminated in this order.
[21] The layer (X1) is a layer formed from a composition containing a resin as a main component,
The layer (Y1) is a layer formed from a composition containing 15% by mass or more of fine particles,
The pressure-sensitive adhesive sheet according to the above [20], wherein the layer (X2) is a layer formed from a composition containing a resin as a main component.
[22] A method for producing the pressure-sensitive adhesive sheet according to any one of [1] to [19], comprising at least the following steps (1) and (2).
Step (1): On the release material (R1), a coating film (x ′) composed of a composition (x) containing a resin as a main component, and a coating composition (y) comprising 15% by mass or more of the fine particles. Step (2) of forming film (y ′): Step of simultaneously drying coating film (x ′) and coating film (y ′) formed in step (1) [23] Adhesion according to [21] above A method for producing a sheet, comprising at least the following steps (1A) and (2A).
Step (1A): A coating film (x1 ′) composed of a composition (x1) containing a resin as a main component on a release material (R1), and a coating film (y) composed of a composition (y) containing 15% by mass or more of fine particles ( Step (2A): A coating film (x1) formed by laminating and forming a coating film (x2 ′) composed of a composition (x2) containing resin as a main component in this order y ′) '), The step of simultaneously drying the coating film (y') and the coating film (x2 ') [24] A method for producing the pressure-sensitive adhesive sheet according to the above [21], comprising at least the following step (1B) and The manufacturing method of an adhesive sheet which has a process (2B).
Step (1B): A coating film comprising a composition (y) containing 15% by mass or more of the fine particles on a layer (X1) mainly containing the resin portion (X) provided on the release material (R1). Step (2B): A coating film (y2) formed by laminating and forming a coating film (x2 ′) composed of a composition (x2) containing a resin as a main component in this order (y ′) ') And coating film (x2') are simultaneously dried

  The pressure-sensitive adhesive sheet of the present invention has excellent air bleedability that can easily remove air pockets that may be generated when it is applied to an adherend, and also has good blister resistance and pressure-sensitive adhesive properties.

It is a cross-sectional schematic diagram of this adhesive sheet which shows an example of a structure of the 1st adhesive sheet of this invention. It is a cross-sectional schematic diagram of this adhesive sheet which shows an example of a structure of the 2nd adhesive sheet of this invention. It is a cross-sectional schematic diagram of this resin layer which shows an example of the shape at the surface (1) side of the resin layer which the adhesive sheet of this invention has. It is a plane schematic diagram of this surface (1) which shows an example of the surface (1) of the resin layer which the adhesive sheet of this invention has. When the surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are affixed, It is a schematic diagram which shows the measuring method of an area ratio. It is a cross-sectional schematic diagram of this resin layer which shows an example of the shape by the side of the surface (2) of the resin layer which the adhesive sheet of this invention has. About the adhesive sheet produced in Example 1, it is an image at the time of observing with a scanning electron microscope after removing peeling material (R1), Comprising: (a) is the surface (1) side vicinity of the resin layer of the said adhesive sheet A cross-sectional image, (b), is a perspective image of the surface (1) of the resin layer of the pressure-sensitive adhesive sheet. About the adhesive sheet produced in Example 1, it is an image at the time of observing with a scanning electron microscope after removing release agent (R1), Comprising: (a) is the surface (from the side surface side of the resin layer of the said adhesive sheet) The perspective image of 1) and (b) are the enlarged images of (a). It is an image at the time of observing the adhesive sheet produced in Example 1 with the scanning electron microscope, (a) is a cross-sectional image of the surface (2) side vicinity of the resin layer of the said adhesive sheet, (b) is the said adhesive FIG. 8 is a perspective image of the surface (2) of the resin layer of the sheet (note that the image in FIG. 8 is based on the surface (2) of the resin layer in order to confirm the presence of a recess on the surface (2) of the resin layer. It was taken and photographed before laminating the material (before the backside treatment). About the adhesive sheet produced in Example 8, it is an image at the time of observing with a scanning electron microscope after removing release agent (R1), Comprising: (a) is a perspective image of the surface (1) of the resin layer of the said adhesive sheet , (B) is a perspective image of the surface (2) of the resin layer of the pressure-sensitive adhesive sheet (in addition, the image of FIG. 9 (b) is for confirming the presence of a recess on the surface (2) of the resin layer, It was obtained by photographing before laminating the base material on the surface (2) of the resin layer (before the back surface treatment). About the adhesive sheet produced in the comparative example 1, it is an image at the time of observing with a scanning electron microscope after removing release agent (R1), Comprising: (a) is a cross-sectional image of the said adhesive sheet, (b) is the said adhesive sheet It is a perspective image of the surface (1) of the resin layer.

In the present invention, for example, the description of “YY including XX component as main component” and “YY mainly composed of XX component” is “the component having the highest content among components included in YY is XX component”. It means that there is. The specific content of the XX component in the description is usually 50% by mass or more with respect to the total amount of YY (100% by mass), but the content of the XX component is preferably It is 65-100 mass%, More preferably, it is 75-100 mass%, More preferably, it is 85-100 mass%.
In the present invention, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
Furthermore, the lower limit value and the upper limit value described in a stepwise manner can be independently combined for a preferable numerical range (for example, a range such as content). For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to make “10 to 60”. You can also.

[Configuration of adhesive sheet]
First, the structure of the adhesive sheet of this invention is demonstrated.
The pressure-sensitive adhesive sheet of the present invention comprises a resin layer (X) containing a resin as a main component on a release material (R1) and a particle part (Y) comprising fine particles, and a substrate on the resin layer. Or if it has a peeling material (R2), it will not restrict | limit in particular.
In the pressure-sensitive adhesive sheet of the present invention, at least the surface (1) of the resin layer on the side on which the release material (R1) is provided (hereinafter also simply referred to as “the surface (1) of the resin layer”) has adhesiveness. .
In the pressure-sensitive adhesive sheet of one embodiment of the present invention, the surface (2) of the resin layer on the side provided with the base material or the release material (R2) (hereinafter, also simply referred to as “surface (2) of the resin layer”). ) May also have adhesiveness. In particular, the pressure-sensitive adhesive sheet in which the surface (2) of the resin layer has adhesiveness and the release material (R2) is laminated on the surface (2) can be an adhesive sheet having adhesiveness on both surfaces.

  Before removing the release material (R1), the pressure-sensitive adhesive sheet according to the present invention is determined depending on whether or not a recess (Z1) having a maximum height difference of 100 nm or more exists on the surface (1) of the resin layer. A "first pressure-sensitive adhesive sheet" having a structure such as the pressure-sensitive adhesive sheets 1a and 1b shown in 1 (a) and (b) and a structure like the pressure-sensitive adhesive sheets 2a and 2b shown in FIGS. 2 (a) and 2 (b) And can be divided into “second pressure-sensitive adhesive sheet”.

  In the pressure-sensitive adhesive sheet of the present invention, the length of the recess (Z1) when the recess (Z1) that appears or exists on the surface (1) is viewed in plan is not particularly limited. That is, the recess (Z1) includes a relatively long groove shape and a relatively short recess shape. Further, the recess (Z2) existing on the surface (2) described later includes a relatively long groove shape and a relatively short recess shape, similarly to the recess (Z1).

Hereinafter, the structure of the 1st adhesive sheet and 2nd adhesive sheet of this invention is demonstrated.
In the following description, “the first pressure-sensitive adhesive sheet of the present invention” and “the second pressure-sensitive adhesive sheet of the present invention” are collectively referred to as “the pressure-sensitive adhesive sheet of the present invention”.

(Configuration of first adhesive sheet)
The first pressure-sensitive adhesive sheet of the present invention has a maximum height of 0.5 μm or more on the surface (2) 122 of the resin layer 12 as the pressure-sensitive adhesive sheets 1a and 1b shown in FIGS. There are a plurality of recesses (Z2) 22 having a difference.
On the other hand, in the first pressure-sensitive adhesive sheet of the present invention, the presence of the recess (Z1) on the surface (1) 121 of the resin layer 12 is not confirmed before the release material (R1) 11 is removed. When the R1) 11 is removed, a plurality of concave portions (Z1) having a maximum height difference of 100 nm or more appear on the surface (1) 121 of the exposed resin layer 12.
In addition, after once removing the release material (R1) 11 of the pressure-sensitive adhesive sheets 1a and 1b in FIG. 1 and causing a plurality of recesses (Z1) to appear on the surface (1) 121 of the resin layer 12, the surface (1 ), The release material (R1) 11 is bonded to the second pressure-sensitive adhesive sheet of the present invention such as the pressure-sensitive adhesive sheets 2a and 2b shown in FIGS. 2 (a) and 2 (b).

As a specific configuration of the first pressure-sensitive adhesive sheet of one embodiment of the present invention, for example, a resin layer 12 and a base material 13 are placed in this order on a release material (R1) 11 as shown in FIG. The pressure-sensitive adhesive sheet 1a having a structure laminated with the above is mentioned.
Moreover, the adhesive sheet 1b which has the structure which laminated | stacked the resin layer 12 and the peeling material (R2) 14 in this order on the peeling material (R1) 11 as shown in FIG.1 (b) may be sufficient.

In the first pressure-sensitive adhesive sheet of the present invention, at least the surface (1) 121 of the resin layer 12 has adhesiveness, but the surface (2) 122 of the resin layer 12 may also have adhesiveness.
If the surface (2) also has adhesiveness, the adhesive sheet 1a shown in FIG. 1 (a) has good adhesion between the resin layer 12 and the substrate 13, and the adhesive sheet shown in FIG. 1 (b). If it is 1b, it can be set as a double-sided adhesive sheet.

(Configuration of second adhesive sheet)
The second pressure-sensitive adhesive sheet of the present invention has a maximum height of 0.5 μm or more on the surface (2) 122 of the resin layer 12 as the pressure-sensitive adhesive sheets 2a and 2b shown in FIGS. 2 (a) and 2 (b). A plurality of recesses (Z2) 22 having a difference exist, and a plurality of recesses (Z1) 21 having a maximum height difference of 100 nm or more exist on the surface (1) 121 of the resin layer 12.

As a specific configuration of the second pressure-sensitive adhesive sheet of one embodiment of the present invention, for example, a resin layer 12 and a base material 13 are provided on a release material (R1) 11 as shown in FIG. The adhesive sheet 2a which has the structure laminated | stacked in order is mentioned.
Moreover, the adhesive sheet 2b which has the structure which laminated | stacked the resin layer 12 and the peeling material (R2) 14 in this order on the peeling material (R1) 11 as shown in FIG.2 (b) may be sufficient.

Moreover, also about the 2nd adhesive sheet of this invention, although at least the surface (1) 121 of the resin layer 12 has adhesiveness, the surface (2) 122 of the resin layer 12 may also have adhesiveness.
If the surface (2) also has adhesiveness, the adhesive sheet 2a shown in FIG. 2 (a) has good adhesion between the resin layer 12 and the substrate 13, and the adhesive sheet shown in FIG. 2 (b). If it is 2b, it can be set as a double-sided adhesive sheet.

The resin layer 12 included in the pressure-sensitive adhesive sheet of the present invention is a layer including a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles.
When the particle part (Y) is contained in the resin layer, the occurrence of blisters can be effectively suppressed when the obtained pressure-sensitive adhesive sheet is used at a high temperature.
The configuration of the distribution of the resin portion (X) and the particle portion (Y) in the resin layer 12 may be a configuration in which the resin portion (X) and the particle portion (Y) are substantially evenly distributed. In particular, it may be configured to be divided into a part mainly composed of the resin part (X) and a part mainly composed of the particle part (Y).
In addition, as shown in FIGS. 1A and 1B and FIGS. 2A and 2B, in the resin layer 12, a portion where the recess (Z2) 22 is formed on the surface (2). The distribution may be such that the proportion of the particle portion (Y) is smaller than the others, or the particle portion (Y) may not be partially present.

In addition, the recessed part (Z2) on the surface (2) of the resin layer which the adhesive sheet of this invention has is, for example, formed by pressing a release material having an embossed pattern on the surface of the resin layer. It is different from a groove having a pre-designed shape as formed by
The concave portion (Z2) is preferably formed by self-forming of the resin layer.
In the present invention, “self-forming” means a phenomenon that creates a disordered shape naturally in the autonomous formation process of the resin layer. It means a phenomenon that naturally forms a disordered shape in the autonomous formation process of the resin layer by drying the coated film.
That is, the recess (Z2) formed by the self-formation of the resin layer is formed in the drying process of the coating film made of the composition that is the material for forming the resin layer.
The shape of the recess (Z2) formed by self-forming the resin layer in this way is adjusted to some extent by adjusting the drying conditions and the type and content of the components in the composition that is the resin layer forming material. However, unlike the groove formed by the transfer of the embossed pattern, it can be said that “it is virtually impossible to reproduce the same shape”.
Moreover, the said recessed part (Z2) is not formed in a predetermined position like the groove | channel formed by transcription | transfer of the embossing pattern using the peeling material etc. to which the embossing pattern was given.

The process of forming the recesses (Z2) on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is considered as follows.
First, at the time of forming a coating film made of a composition containing fine particles as a material for forming the particle portion (Y), fine particles are present randomly in the coating film.
Here, in the step of drying the coating film, shrinkage stress is generated inside the coating film, and cracks are generated in the coating film at a portion where the binding force of the resin, which seems to be caused by the presence of fine particles, is weakened. And it is thought that resin (Z2) is formed on the surface (2) of a resin layer because resin around this crack part flows into the space temporarily generated by the crack.
In addition, in the drying process of the coating film, when cracks occur in the coating film, the fine particles that were originally present are pushed away to other parts, so the particle part (Y2) where the recess (Z2) is formed ) May be less than others.

Further, the first pressure-sensitive adhesive sheet of the present invention has a surface (1) due to the presence of a plurality of recesses (Z2) formed on the surface (2) of the resin layer and the uneven distribution of fine particles in the resin layer. ) Is considered to have a partially non-uniform distribution. Therefore, it is considered that the recess (Z1) appears on the surface (1) of the resin layer when the release material (R1) is removed from the first pressure-sensitive adhesive sheet of the present invention.
Therefore, the recess (Z1) that appears or exists on the surface (1) of the resin layer included in the first and second pressure-sensitive adhesive sheets of the present invention is, for example, a release material having an embossed pattern on the surface of the resin layer. It is different from a groove having a shape designed in advance, which is formed by transferring an emboss pattern such as pressing.
That is, the shape of the recess (Z1) is different from the groove formed by the transfer of the embossed pattern, as in the case of the recess (Z2).
Moreover, the said recessed part (Z1) is not formed in a predetermined position like the groove | channel formed by transcription | transfer of the embossing pattern using the peeling material etc. to which the embossing pattern was given.

In addition, the concave portion (Z2) separately forms, for example, a coating film made of a composition having a large amount of fine particles and a small resin content, and a coating film made of a composition containing a resin as a main component, It is easy to form by drying these two coating films simultaneously. By forming the recess (Z2), the recess (Z1) is likely to appear on the surface (1) when the release material (R1) is removed.
After forming two-layer coating films with different resin contents, the two-layer coating films are dried at the same time, resulting in a shrinkage stress difference inside the coating film and causing cracks in the coating film. It will be easier.

In addition, from the viewpoint of facilitating the formation of the recess (Z2) and facilitating the appearance of the recess (Z1) on the surface (1), it is preferable to adjust the following matters as appropriate. It is considered that factors due to these matters act in a complex manner so that the recess (Z2) is easily formed and the recess (Z1) is likely to appear.
Incidentally, preferred embodiments of each item for facilitating the formation of the recess (Z2) and the appearance of the recess (Z1) on the surface (1) are as described in the corresponding item described later.
-The type of resin, constituent monomer, molecular weight, and content contained in the composition that is the coating film forming material.
-The kind of crosslinking agent and the kind of solvent which are contained in the composition which is a film-forming material.
-Viscosity and solid content concentration of the composition which is a material for forming the coating film.
-Shape, type and mass concentration of fine particles.
-Composition of coating film forming material, dispersion state of fine particles in coating film, content of fine particles.
-The thickness of the coating film to be formed. (In the case of multiple layers, the thickness of each coating film)
-Drying temperature and drying time of the formed coating film.

In the formation of the pressure-sensitive adhesive layer of a general pressure-sensitive adhesive sheet, the above items are often set appropriately for the purpose of forming a pressure-sensitive adhesive layer having a flat surface.
On the other hand, in the present invention, when the concave portion (Z2) is intentionally formed and the release material (R1) is removed, the concave portion (Z1) that can contribute to the improvement of the air release property of the pressure-sensitive adhesive sheet on the surface (1). The above-mentioned matters are set so as to appear, and this is completely different from a general method for designing an adhesive layer of an adhesive sheet.

The above items are preferably set as appropriate in consideration of the fluidity of fine particles and resin contained in the coating film to be formed.
For example, by adjusting the viscosity of a coating film made of a composition containing a large amount of fine particles to an appropriate range, while maintaining the predetermined fluidity of the fine particles in the coating film, other coating films (containing a large amount of resin) The mixing with the coating film) can be moderately suppressed. By adjusting in this way, in the coating film containing a lot of resin, cracks are generated in the horizontal direction, and the recesses (Z2) tend to be easily formed.
As a result, the ratio of the formed recesses (Z2) on the surface (2) can be increased, the ratio of the recesses (Z2) connected to each other can be increased, and the release material (R1) is removed. The recess (Z1) is likely to appear on the surface (1).

Moreover, among the above matters, it is preferable to appropriately adjust the type, constituent monomer, molecular weight, and resin content of the resin so that the resin contained in the coating film containing a large amount of resin has appropriate viscoelasticity.
In other words, by appropriately hardening the hardness of the coating film (hardness determined by factors such as the viscoelasticity of the resin and the viscosity of the coating solution), the shrinkage stress of the resin portion (X) is increased, and the recess (Z2) is formed. It becomes easy to form. The harder the coating film, the stronger the shrinkage stress and the easier it is to form the recesses (Z2). Further, if the elasticity of the resin is increased too much, the adhesive strength of the resin layer formed from the coating film tends to decrease. Considering this point, it is preferable to appropriately adjust the viscoelasticity of the resin.
In addition, by appropriately selecting the fine particles, resin, etc., and adjusting the dispersion state of the fine particles, the degree of swelling of the resin layer thickness by the fine particles and the self-forming force of the recesses (Z2) are adjusted, As a result, it is considered that the recess (Z2) can be easily formed on the surface (2) and can be adjusted.

Furthermore, it is preferable to appropriately set the above items in consideration of the crosslinking rate of the formed coating film (or composition that is a forming material).
That is, when the crosslinking speed of the coating film is too high, the coating film may be cured before the recess (Z2) is formed. It also affects the size of cracks in the coating.
The crosslinking rate of the coating film can be adjusted by appropriately setting the type of the crosslinking agent and the solvent in the composition as the forming material, the drying time and the drying temperature of the coating film.

(Recess (Z1))
In the first pressure-sensitive adhesive sheet of the present invention, when the release material (R1) is removed, a plurality of concave portions (Z1) appear on the surface (1) of the exposed resin layer, whereas the present invention The second pressure-sensitive adhesive sheet has a plurality of recesses (Z1) on the surface (1) of the resin layer, regardless of whether or not the release material (R1) is removed.
In the first and second pressure-sensitive adhesive sheets of the present invention, the concave portion (Z1) that appears or exists on the surface (1) of the resin layer satisfies the following requirements (Ia) to (IIa).
Requirement (Ia): A plurality of concave portions (Z1) having a maximum height difference of 100 nm or more appear or exist in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1).
Requirement (IIa): 95% or more of the plurality of recesses (Z1) appearing or existing in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) are different from each other. It has a shape.
In addition, the first and second pressure-sensitive adhesive sheets of the present invention preferably further satisfy one or more of the following requirements (IIIa), requirements (IVa), and requirements (Va), and satisfy all requirements: Is more preferable.
Requirement (IIIa): When the release material (R1) is removed and the surface (1) of the exposed resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted, the surface ( The area ratio of the pasting part with the smooth surface of the translucent adherend in 1) is 60 to 99.999%.
Requirement (IVa): A plurality of concave portions (Z1) appear or exist irregularly on the surface (1) of the resin layer.
Requirement (Va): The shape of the pasting surface on the exposed surface (1) of the resin layer is indefinite.
Hereinafter, the requirements (Ia) to (Va) will be described in detail.

<Requirement (Ia)>
FIG. 3 is a schematic cross-sectional view of the resin layer showing an example of the shape on the surface (1) side of the resin layer of the pressure-sensitive adhesive sheet of the present invention.
On the surface (1) 121 of the resin layer 12 of the pressure-sensitive adhesive sheet of the present invention, a plurality of concave portions (Z1) 21 appear or exist as shown in FIG.
Like the concave portion (Z1) 21 shown in FIG. 3A, the shape of the normal concave portion (Z1) includes two peak portions (M ₁ ), (M ₂ ), a valley portion (N), and Have In the present invention, the “maximum height difference” of the recess (Z1) is the highest position (m) of the two peak portions (M ₁ ) and (M ₂ ) with respect to the thickness direction of the resin layer 12 (FIG. 3 (a), the length of the difference (H ₁ ) between the peak portion (M ₁ ) maximum point and the lowest position (n) (the minimum point of the valley portion (N) in FIG. 3 (a)). means.
In the case as shown in FIG. 3B, a recess (Z1) 211 having two peak portions (M ₁₁ ) and (M ₁₂ ) and a valley portion (N ₁ ), and two peak portions (M ₁₂ ) and (M ₁₃ ), and a recess (Z1) 212 having a valley portion (N ₂ ). In this case, the length of the difference (H ₁₁ ) between the maximum point of the peak portion (M ₁₁ ) and the minimum point of the valley portion (N ₁ ) represents the maximum height difference of the concave portion (Z 1) 211, and the peak portion (M ₁₃ ) And the minimum point of the valley portion (N ₂ ) (H ₁₂ ) represents the maximum height difference of the recess (Z 1) 212.

In the pressure-sensitive adhesive sheet of the present invention, the “recess (Z1)” that appears or exists on the surface (1) refers to a recess having a maximum height difference of 100 nm or more. As the “concave portion (Z1)” defined in the present invention, it is sufficient that a portion having a maximum height difference of 100 nm or more is included in any portion of the concave portion (Z1), and covers the entire region of the concave portion (Z1). It is not necessary to have a height difference of the maximum height difference value.
In addition, whether or not there are a plurality of recesses (Z1) that satisfy the requirement (Ia) appears or exists is surrounded by a square of 5 mm on an arbitrarily selected side on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet. The determination is made by observing the inside of the region (P1) with an electron microscope. More specifically, the determination is made by the method described in the examples.

  The maximum height difference of the single concave portion (Z1) is 100 nm or more. From the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet, maintaining the appearance of the pressure-sensitive adhesive sheet, and the shape stability of the pressure-sensitive adhesive sheet. From the viewpoint, the thickness is preferably 200 nm or more and less than the thickness of the resin layer, more preferably 300 nm and less than the thickness of the resin layer, and still more preferably 500 nm or more and less than the thickness of the resin layer.

  The ratio of the maximum value of the maximum height difference values of the plurality of recesses (Z1) appearing or existing in the region (P1) to the thickness of the resin layer [maximum value of the maximum height difference / thickness of the resin layer. ] Is preferably 0.1 / 100 to 100/100, more preferably 0.8 / 100 to 50/100, still more preferably 1.2 / 100 to 30/100, still more preferably 2.0 / 100. 100 to 20/100.

Moreover, as an average value of the width | variety of the said recessed part (Z1), from a viewpoint of the improvement of the air release property of an adhesive sheet, and a viewpoint of making the adhesiveness of an adhesive sheet favorable, Preferably it is 1-2000 micrometers, More preferably, it is 3 ˜1500 μm, more preferably 5˜1000 μm.
In the present invention, the width of the concave portion (Z1) means the distance between the maximum points of the two peak portions. In the concave portion (Z1) 21 shown in FIG. It refers to the distance L ₁ between M ₁ ) and the mountain portion (M ₂ ). Further, in the recess (Z1) 211 shown in FIG. 3 (b) refers to the distance _{L 11} between the peak portions _{(M 11)} and the peak portions _{(M 12),} in recesses (Z1) 212 is the peak portions The distance L ₁₂ between (M ₁₂ ) and the mountain portion (M ₁₃ ) is indicated.
In addition, when the pressure-sensitive adhesive sheet of the present invention is viewed in plan (when viewed from directly above), when the concave portion (Z1) has a long side and a short side, the short side is referred to as a width.

Ratio of the maximum height difference and the average width of the single recess (Z1) [maximum height difference / average width] (in the recess (Z1) 21 shown in FIG. 3A, “H ₁ / L ₁ ”) is preferably from 1 / 300,000 to 1500/1, more preferably from 1 / 50,000 from the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet and improving the pressure-sensitive adhesive property of the pressure-sensitive adhesive sheet. It is -500/1, More preferably, it is 1 / 15000-150 / 1.

The concave portion (Z1) that appears or exists on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is for releasing the “air pocket” that occurs when the pressure-sensitive adhesive sheet of the present invention is stuck to the adherend to the outside. It plays a role as an air discharge passage.
Normally, the recess (Z1) having a relatively small maximum height difference as described above is difficult to play a role as an air discharge passage for escaping the “air reservoir” to the outside. However, in the pressure-sensitive adhesive sheet of the present invention, the resin layer is easily deformed because a plurality of predetermined recesses (Z2) are also present on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet. That is, when an “air pool” occurs when the surface (1) is stuck to the adherend, the concave portion (Z1) on the surface (1) can escape the air pool to the outside by the pressure of the air pool. Deforms to a certain size and functions as an air discharge passage.

<Requirement (IIa)>
The pressure-sensitive adhesive sheet of the present invention has a shape in which 95% or more of the plurality of concave portions (Z1) appearing or existing in the region (P1) on the surface (1) are different from each other as described in the requirement (IIa). Yes.
FIG. 4 shows an example of a schematic plan view of the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of the present invention. As shown in FIG. 4, 95% or more of the plurality of recesses (Z1) 21 that appear or exist on the surface (1) 121 of the resin layer 12 of the pressure-sensitive adhesive sheet of the present invention have different shapes.
In terms of whether or not the requirement (IIa) is satisfied, for example, grooves described in a predetermined pattern determined in a predesigned shape are formed on the surface of the pressure-sensitive adhesive layer as described in Patent Document 1 above. The pressure sensitive adhesive sheet and the pressure sensitive adhesive sheet of the present invention are clearly distinguished.

Conventionally known pressure-sensitive adhesive sheet having a pre-designed shape on the surface of the pressure-sensitive adhesive layer and having grooves arranged on the surface in a predetermined pattern determined by the groove shape and groove arrangement, Even if one characteristic selected from air bleedability, appearance, adhesion characteristics, punching workability, and the like is improved, the other characteristics often deteriorate.
The inventors of the present invention, for example, paying attention to the fact that the shape of the groove contributing to the improvement of the air release property and the shape of the groove contributing to the improvement of the adhesive property are different from each other, and satisfying the requirement (IIa) The technical significance of was found.
That is, in the pressure-sensitive adhesive sheet of the present invention, the plurality of concave portions (Z1) having different shapes that appear or exist in the region (P1) on the surface (1) of the resin layer have air release properties, appearance, pressure-sensitive adhesive properties, Also, the degree of contribution to the improvement of the punching processability is different. Therefore, by forming a plurality of recesses having different degrees of contribution to various characteristics, it is possible to obtain an adhesive sheet that improves these characteristics in a well-balanced manner.

  In the pressure-sensitive adhesive sheet of one embodiment of the present invention, the ratio of the plurality of concave portions (Z1) having different shapes that appear or exist in the region (P1) on the surface (1) of the resin layer is the region (P1). ) Is preferably 98% or more, and more preferably 100%, with respect to the total number of recesses (100%).

In the present invention, whether or not the above requirement (IIa) is satisfied is determined by arbitrarily selecting a region (P1) surrounded by a square of 5 mm on each side on the surface (1) of the resin layer of the target adhesive sheet. ) The shape of the plurality of recesses (Z1) that appeared or existed in each is observed with an electron microscope (magnification: 30 to 100 times), and the total number of the recesses (Z1) in the region (P1) (100%), if the number of recesses (Z1) having different shapes is 95% or more (preferably 98% or more, more preferably 100%), the recesses (Z1 satisfying the above requirement (IIa) ) Is a pressure-sensitive adhesive sheet having a resin layer present on the surface (1).
The observation of the shape of the plurality of recesses (Z1) described above may be a method of directly observing with an electron microscope at the above magnification, and an image is acquired using the electron microscope at the above magnification and is shown in the image. A method of visually observing the shape of the plurality of recesses may be used. More specifically, the determination is made based on the method described in the examples.
Here, “the number of recesses (Z1) having different shapes is 100%” means “all of the plurality of recesses (Z1) observed in the region (P1) have different shapes. "Means.

In this specification, a recess continuously connected without interruption in a selected region is counted as “one recess”.
For example, even if two concave portions existing in the selected region are combined in another region adjacent to the region and formed as one concave portion, the two in the selected region The individual recesses are counted as independent ones.
For example, in a region (P1) surrounded by a square 50 having a side of 5 mm arbitrarily selected on the surface (1) 121 of the resin layer 12 shown in FIG. (Z1) 21 and 210 exist.

  In the pressure-sensitive adhesive sheet of the present invention, the number of the concave portions (Z1) appearing or existing in a region (P1) surrounded by a square of 5 mm on each side arbitrarily selected on the surface (1) of the resin layer is 2 or more. However, it is preferably 3 or more, more preferably 4 or more, from the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet, and preferably 20,000 from the viewpoint of maintaining good appearance and adhesive properties. Below, more preferably 10,000 or less.

Further, from the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet, as shown in FIG. 4A, a region surrounded by an arbitrarily selected square 50 having a side of 5 mm on the surface (1) 121 of the resin layer 12 It is preferable that one or more of the recesses (Z1) 21 and 210 appearing or existing in (P1) extend to any side of the square 50 having a side of 5 mm, which is a boundary line of the region (P1).
In addition, on the surface (1) 121 of the resin layer 12 of the pressure-sensitive adhesive sheet shown in FIG. 4A, the recesses (Z1) 21 and 210 extend to form a square 50 having a side of 5 mm, which is a boundary line of the region (P1). There are 20 intersections 21a in total with any side.
The number of intersections between any side of a square having a side of 5 mm that is the boundary line between the recess (Z1) and the region (P1) is preferably 1 or more, more preferably 2 or more, More preferably, the number is 3 or more.

In addition, from the viewpoint of obtaining a pressure-sensitive adhesive sheet with improved air detachability, a concave portion (Z1) that appears or exists in the region (P1) on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention. It is preferable that one or more of these have a shape extending continuously into one or more other regions (P1 ′) surrounded by a square with a side of 5 mm adjacent to the region (P1). More preferably, the shape extends continuously into the region (P1 ′), and more preferably the shape extends continuously into the other region (P1 ′).
For example, in FIG. 4B, when attention is paid to a region (P1) surrounded by a square 50 having a side of 5 mm arbitrarily selected on the surface (1) 121 of the resin layer 12, “the region (P1) And the other region (P1 ′) surrounded by a square with a side of 5 mm ”is a region (P1′-1) surrounded by a square 501 with a side of 5 mm, and a region (P1′-1) surrounded by a square 502 with a side of 5 mm ( P1′-2), a region (P1′-3) surrounded by a square 503 having a side of 5 mm, and a region (P1′-4) surrounded by a square 504 having a side of 5 mm.

Further, focusing on the “recess (Z1) 210” on the surface (1) 121 of the resin layer 12 shown in FIG. 4B, the “recess (Z1) 210” is surrounded by a square 50 having a side of 5 mm. The concave portion (Z1) that appears or exists in the region (P1), but in the region (P1′-2) surrounded by the square 502 with a side of 5 mm adjacent to the region (P1), and with a side of 5 mm It has a shape extending into the region (P1′-3) surrounded by the square 503.
Like the “recess (Z1) 210” shown in FIG. 4B, it has a shape extending not only within the region (P1) but also to another region (P1 ′) adjacent to the region (P1). When the concave portion (Z1) appears or exists on the surface (1), the pressure-sensitive adhesive sheet is further improved in air bleeding.

Further, the recess (Z1) appearing or existing in the region (P1) on the surface (1) of the resin layer is not only one or more other regions (P1 ′) adjacent to the region (P1), but also other It is preferable that the shape further extends continuously to the region (P1 ″) other than the region (P1 ′) adjacent to the region (P1 ′).
For example, the “concave portion 210” shown in FIG. 4B is not only the region (P1′-2) adjacent to the region (P1) but also the region (P1′−) adjacent to the region (P1′-2). 5) also has a continuous extended shape.

<Requirement (IIIa)>
The pressure-sensitive adhesive sheet according to one embodiment of the present invention has a surface (1) when the surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are attached as described in the requirement (IIIa). ) The area ratio of the pasting part (hereinafter also simply referred to as “pasting part” or “pasting part on the surface (1)”) with the smooth surface of the translucent adherend is 60 to 99.999%. Is preferred.
Here, if the area ratio of the said sticking part is 60% or more, the adhesive surface of the surface (1) of a resin layer and a to-be-adhered body can be ensured, and an adhesive characteristic can be made favorable. In addition, it is possible to prevent adverse effects such as occurrence of peeling, and to obtain a pressure-sensitive adhesive sheet having an excellent appearance.
On the other hand, if the area ratio of the affixed portion is 99.999% or less, the pressure-sensitive adhesive sheet can be made excellent in air-releasing properties, and air pockets that can be generated when the adhesive sheet is affixed to an adherend are easy. Can be removed.
From the above viewpoint, the ratio of the area to be adhered to the adherend is preferably 70 to 99.999%, more preferably 80 to 99.996%, still more preferably 85 to 99.993%, and still more preferably. 90 to 99.990%.

In addition, the “translucent adherend having a smooth surface” described in the requirement (IIIa) is an adherend used in the measurement of the area ratio of the affixed portion on the surface (1) specified by the requirement. It merely defines the adherend to which the pressure-sensitive adhesive sheet of the present invention is to be attached.
The adherend to which the pressure-sensitive adhesive sheet of the present invention is applied is not particularly limited as to whether it has a smooth surface or translucency. For example, it may be a non-transparent adherend comprising a curved surface. Good.

The “smooth surface” described in the requirement (IIIa) means that the center line average roughness (Ra ₇₅ ) defined by JIS B0601: 2001 is less than 0.1 μm (preferably 0.02 μm or less, more preferably 0.01 μm). Means the following):
The “translucency” described in the requirement (IIIa) means a characteristic that the total light transmittance measured in accordance with JIS K7105 is 70% or more.
The material for forming the light-transmitting adherend described in requirement (IIIa) is not particularly limited, but glass is preferable from the viewpoint that it is easy to obtain a light-transmitting adherend having a smooth surface as defined above.

  In the present invention, on the surface (1), 5 regions are selected as “regions surrounded by a square with an arbitrarily selected side of 1 to 10 mm”, and the value of the area ratio of the pasted portion in each region is as follows: The average value of the area ratio of the applied part obtained by the operations (i) to (iii) can be regarded as the “area ratio of the applied part on the surface (1)” of the pressure-sensitive adhesive sheet to be measured. . In addition, more specifically, the average value of the area ratio of the applied part calculated by the method described in the examples is regarded as “the area ratio of the applied part on the surface (1)” of the pressure-sensitive adhesive sheet to be measured. You can also.

Operation (i): As shown in FIG. 5A, the surface (1) 121 of the resin layer 12 of the target adhesive sheet is provided on the smooth surface 101a of the translucent adherend 101 made of glass or the like. Leave to touch. Then, the surface of the resin layer 12 is reciprocated 5 times with a 2 kg roller (crimping device defined in JIS Z 0237: 2000 10.2.4) with respect to the base material or release material side of the pressure-sensitive adhesive sheet. 121 and the smooth surface 101a of the translucent adherend 101 are attached. And the laminated body 100 installed in the direction as shown to Fig.5 (a) is obtained.
Operation (ii): From the translucent adherend 101 side of the laminate 100 obtained in operation (i), an arbitrarily selected region on the surface (1) 121 is obtained using a digital microscope as shown in FIG. The interface between the smooth surface 101a of the translucent adherend 101 and the surface (1) 121 of the resin layer is photographed from the W direction of a), and a digital image of the selected region is obtained.
Operation (iii): Based on the obtained digital image, image processing (binarization processing) is performed using image analysis software to obtain a binarized image. Then, based on the binarized image, the area S of the pasting portion in contact with the smooth surface of the translucent adherend in the entire area of the selected region is obtained. Then, based on the calculation formula “[area ratio (%) of affixed part] = S / total area of the selected area × 100”, the area ratio of the affixed part with the translucent adherend in the selected area is calculated. calculate.
In addition, the kind of translucent to-be-adhered body used for a measurement and the specific method of operation (i)-(iii) are as having described in the Example.

As the digital microscope, for example, product names “Digital Microscope VHX-1000” and “Digital Microscope VHX-5000” manufactured by Keyence Corporation can be used. Further, the area to be observed may be increased according to the measurable magnification of the digital microscope, and the area ratio (%) of the affixed portion per 1 mm ² may be calculated.

Here, an example of the shape of the pasting part in the surface (1) will be described.
For example, as shown in FIG. 5A, the surface (1) of a region (P1) surrounded by a square 50 having a side of 5 mm on the surface (1) 121 of the resin layer shown in FIG. ) 121 and the smooth surface 101a of the translucent adherend 101 are affixed and viewed in a plan view from the W direction on the translucent adherend 101 side in the region (P1) of FIG. Consider the shape of the affixed part as an example.
FIG. 5B is a diagram schematically showing an example of the shape of the pasted portion in the selected region (P1).
Comparing the translucent adherend shown in FIG. 5 (b) with the schematic diagram in the region (P1) after application and the schematic diagram in the region (P1) shown in FIG. 4 (a), FIG. The non-sticking part 51 with the translucent to-be-adhered body in 5 (b) may become smaller than the part which the recessed part (Z1) 21 in the area | region (P1) of FIG. 4 (a) occupies. This is because the surface (1) has adhesiveness, but when the surface (1) is affixed to the translucent adherend, a part of the concave portion (Z1) having a relatively small height difference is formed. This is because it was stuck in contact with the smooth surface of the translucent adherend.
That is, the shape of the non-sticking portion 51 with the smooth surface of the translucent adherend shown in FIG. 5B does not match the shape of the portion occupied by the recess (Z1) 21 shown in FIG. There is a case.
In addition, in FIG.5 (b), the non-sticking part 51 with the smooth surface of a translucent to-be-adhered body is a location where a height difference is large also in the structure of the recessed part (Z1) 21. Therefore, it can be said that the greater the proportion of the non-sticking portion 51, the higher the effect of air release that allows the “air pocket” to escape to the outside.

Further, in FIG. 5B, from the viewpoint of forming a pressure-sensitive adhesive sheet with improved air bleeding, the surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted. In this case, the shape of the affixed portion 52 with the smooth surface of the translucent adherend on the surface (1) of the resin layer (hereinafter, also simply referred to as “the affixed portion shape”) is the translucent adherend side. It is preferable that it can be visually recognized.
Note that whether or not the shape of the pasted portion can be visually confirmed is determined by visually observing the laminated body 100 of FIG. 5A obtained from the above-described operation (i) from the W direction. It can be judged by whether or not can be confirmed.

Furthermore, in the pressure-sensitive adhesive sheet of one embodiment of the present invention, the surface (1) of the resin layer and When the smooth surface of the translucent adherend having a smooth surface is affixed, the shape of the affixed portion of the surface (1) of the resin layer with the smooth surface of the adherend may be indefinite. preferable.
As shown in FIG. 5B, “the shape of the affixed portion is indefinite” means that the shape of the affixed portion when the shape of the affixed portion is viewed in plan is surrounded by only a circle or a straight line ( This means a shape that does not have a specific shape such as a triangle, a quadrangle, etc., has no regularity in shape, and does not show similarities in the shapes of individual pasted portions. That is, the shape of the sticking surface formed by transferring the emboss pattern such as pressing the release material having the emboss pattern against the surface of the resin layer cannot be said to be “indeterminate”.

Note that whether or not the shape of the pasted portion is indeterminate is determined by visually observing the laminated body 100 obtained by the above-described operation (i) from the direction W in FIG. 5A or using a digital microscope. Is the principle.
However, in the same manner as the method for calculating the area ratio of the pasted portion, five areas are selected on the surface (1) and the “area surrounded by a square of 1 to 10 mm on an arbitrarily selected side”, and the above operations (i) and The determination can also be made based on the five types of digital images acquired in (ii). That is, by observing the shape of the affixed part in each area indicated in each digital image and determining that the affixed part has an indeterminate shape in any of the five areas of the digital image, the “adhesion of the adhesive sheet” It can also be considered that the shape of the portion is indefinite.

<Requirement (IVa)>
As for the adhesive sheet of 1 aspect of this invention, it is preferable that several recessed part (Z1) appears irregularly or exists on the surface (1) of a resin layer as said requirement (IVa).
In the present invention, "a plurality of recesses (Z1) appear or exist irregularly on the surface (1) of the resin layer" means that a plurality of recesses (Z1 appearing or existing on the surface (1) of the resin layer. ) Position does not have the same repeating pattern and is irregular (random) (a state in which a plurality of concave portions (Z1) appear or have no periodicity at a position). In other words, like the groove described in Patent Document 1, that is, the groove formed by transferring the emboss pattern such as pressing the release material having the emboss pattern against the surface of the resin layer, the “arrangement” Is different from the state of
When the plurality of concave portions (Z1) appear or exist irregularly on the surface (1) of the resin layer, it is possible to provide a pressure-sensitive adhesive sheet in which various properties such as air leakage and pressure-sensitive adhesive properties are improved in a well-balanced manner.

Note that whether or not “a plurality of recesses (Z1) appear or appear irregularly on the surface (1) of the resin layer” is determined on the surface (1) of the resin layer of the target adhesive sheet. Or, in principle, the position of the plurality of concave portions (Z1) present is determined by visual observation or observation with a digital microscope or an electron microscope (magnification: 30 to 100 times).
However, an arbitrarily selected region (preferably, a region (P1) surrounded by a square of 5 mm on a side) on the surface (1) and surrounded by a square of 1 to 10 mm on a side appears in the region. Or you may judge by observing the position of the several recessed part (Z1) which exists with a digital microscope or an electron microscope (magnification: 30-100 times). In other words, if there is no regularity in the “positions of the plurality of recesses (Z1)” that appear or exist in the selected area, the target adhesive sheet is considered to satisfy the requirement (IV). Can do.
Further, the observation of the positions of the plurality of concave portions (Z1) may be a method of directly observing with a digital microscope or an electron microscope at the above magnification, and acquiring an image using the digital microscope or the electron microscope at the above magnification, A method of visually observing the positions of the plurality of recesses (Z1) shown in the image may be used.

<Requirement (Va)>
As for the adhesive sheet of 1 aspect of this invention, it is preferable that the shape of the sticking surface on the surface (1) which the resin layer exposed is an indefinite shape as the said requirement (Va).
In the present invention, “the shape of the sticking surface on the exposed surface (1)” means that the release material (R1) is removed, and a plurality of appearing or existing on the exposed surface (1) of the resin layer. It is the surface except the range which a recessed part (Z1) occupies.
In the schematic plan view shown in FIG. 4A, the “sticking surface” refers to a shaded portion of the surface (1) 121 of the resin layer excluding a plurality of recesses (Z1).
Further, “the shape of the affixed surface is indefinite” means that the affixed surface shape is only a circle or a straight line like the shape of the shaded portion of the surface (1) 121 of the resin layer shown in FIG. It means that the shape does not have a specific shape such as an enclosed shape (triangle, square, etc.) and does not have a predetermined repetitive pattern. That is, the shape of the pasting surface formed by transferring the emboss pattern such as pressing the release material having the emboss pattern against the surface of the resin layer is excluded.
In other words, in the pressure-sensitive adhesive sheet that satisfies the requirements (IIa) and (IV), the shape of the sticking surface on the surface (1) of the resin layer is considered to be indefinite.
Since the shape of the sticking surface on the surface (1) where the resin layer is exposed is indeterminate, it is possible to obtain a pressure-sensitive adhesive sheet in which various properties such as air release and pressure-sensitive adhesive properties are improved in a well-balanced manner.

Whether or not “the shape of the sticking surface on the surface (1) is indefinite” is determined by visually or digitally examining the shape of the sticking surface on the surface (1) of the resin layer of the target adhesive sheet. In principle, it is determined by observation with an electron microscope (magnification: 30 to 100 times).
However, an arbitrarily selected area on the surface (1) surrounded by a square having a side of 1 to 10 mm (preferably, an area (P1) surrounded by a square having a side of 5 mm) is present in the area. You may judge by observing the shape of the sticking surface to observe with a digital microscope or an electron microscope (magnification: 30-100 times). That is, when it is determined that the “shape of the pasting surface” in the selected region is indefinite, the target adhesive sheet can be regarded as satisfying the requirement (V).
Further, the observation of the shape of the affixed surface may be a method of directly observing with a digital microscope or an electron microscope at the above magnification, and an image is obtained using the digital microscope or the electron microscope at the above magnification and shown in the image. A method of visually observing the shape of the applied surface is also possible.

(Recess (Z2))
In the first and second pressure-sensitive adhesive sheets of the present invention, the recess (Z2) present on the surface (2) of the resin layer satisfies the following requirements (Ib) and (IIb).
Requirement (Ib): There are a plurality of concave portions (Z2) having a maximum height difference of 0.5 μm or more in a region (P2) surrounded by a square of 5 mm on an arbitrarily selected side on the surface (2).
Requirement (IIb): 95% or more of the plurality of recesses (Z2) existing in a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) have different shapes. doing.
Moreover, it is preferable that the first and second pressure-sensitive adhesive sheets of the present invention further satisfy one or more of the following requirements (IIIb), requirements (IVb), and requirements (Vb), and satisfy all the requirements. Is more preferable.
Requirement (IIIb): One or more recesses (Z2) exist in a region (Q2) surrounded by a square of 1 mm on an arbitrarily selected side on the surface (2).
Requirement (IVb): A plurality of concave portions (Z2) are irregularly present on the surface (2) of the resin layer.
Requirement (Vb): On the surface (2) of the resin layer, the surface shape excluding the plurality of recesses (Z2) is indefinite.
Hereinafter, the requirements (Ib) to (Vb) will be described in detail.

<Requirement (Ib)>
FIG. 6 is a schematic cross-sectional view of the resin layer showing an example of the shape on the surface (2) side of the resin layer of the pressure-sensitive adhesive sheet of the present invention.
On the surface (2) 122 of the resin layer 12 of the pressure-sensitive adhesive sheet of the present invention, there are a plurality of recesses (Z2) 22 as shown in FIG.
Like the concave portion (Z2) 22 shown in FIG. 6A, the shape of the normal concave portion (Z2) includes two peak portions (M ₁ ), (M ₂ ), a valley portion (N), and Have In the present invention, the “maximum height difference” of the recess (Z2) is the highest position (m) of the two peak portions (M ₁ ) and (M ₂ ) with respect to the thickness direction of the resin layer 12 (FIG. 6 (a), the length of the difference (H ₂ ) between the peak portion (M ₁ ) maximum point and the lowest position (n) (the minimum point of the valley portion (N) in FIG. 6 (a)). means.
In the case of FIG. 6B, a recess (Z2) 221 having two peak portions (M ₁₁ ) and (M ₁₂ ) and a valley portion (N ₁ ), and two peak portions (M ₁₂ ), (M ₁₃ ), and a recess (Z2) 222 having a valley portion (N ₂ ). In this case, the length of the difference (H ₂₁ ) between the maximum point of the peak portion (M ₁₁ ) and the minimum point of the valley portion (N ₁ ) represents the maximum height difference of the recess (Z 2) 221, and the peak portion (M ₁₃ ) And the minimum point of the valley portion (N ₂ ) (H ₂₂ ) represent the maximum height difference of the recess (Z 2) 222.

In the pressure-sensitive adhesive sheet of the present invention, the “recess (Z2)” present on the surface (2) refers to a recess having a maximum height difference of 0.5 μm or more. As the “concave portion (Z2)” defined in the present invention, a portion having a maximum height difference of 0.5 μm or more may be included in any portion of the concave portion (Z2). It is not necessary to have a height difference of the maximum height difference value over the region.
In addition, the determination of whether or not there are a plurality of recesses (Z2) that satisfy the requirement (Ib) is based on a region (5 mm) of an arbitrarily selected side (5 mm) on the surface (2) of the resin layer of the adhesive sheet ( The determination is made by observing the inside of P2) with an electron microscope. More specifically, the determination is made by the method described in the examples.

  The maximum height difference of the single concave portion (Z2) is 0.5 μm or more. From the viewpoint of improving the air release property of the pressure-sensitive adhesive sheet, maintaining the appearance of the pressure-sensitive adhesive sheet well, and stabilizing the shape of the pressure-sensitive adhesive sheet. From the viewpoint of safety, the thickness is preferably 1.0 μm or more and less than the thickness of the resin layer, more preferably 3.0 μm or more and the thickness of the resin layer or less, and further preferably 5.0 μm or more and the thickness of the resin layer or less. .

  The ratio of the maximum value of the maximum height difference values of the plurality of recesses (Z2) existing in the region (P2) to the thickness of the resin layer [maximum value of maximum height difference / thickness of the resin layer] Is preferably 1/100 to 100/100, more preferably 5/100 to 99/100, still more preferably 10/100 to 96/100, and still more preferably 15/100 to 90/100.

Moreover, as an average value of the width | variety of the said recessed part (Z2), Preferably it is 1-500 micrometers, More preferably, it is 3-400 micrometers, More preferably, it is 5-300 micrometers.
In the present invention, the width of the concave portion (Z2) means the distance between the maximum points of the two peak portions. In the concave portion (Z2) 22 shown in FIG. It refers to the distance L ₂ between M ₁ ) and the mountain portion (M ₂ ). Further, in the recess (Z2) 221 shown in FIG. 5 (b) refers to the peak portions _{(M 11)} and the peak portions _{(M 12)} the distance between the _{L 21,} the recess (Z2) 222 is the peak portions The distance L ₂₂ between (M ₁₂ ) and the mountain portion (M ₁₃ ) is indicated.
In addition, when the pressure-sensitive adhesive sheet of the present invention is viewed in plan (when viewed from directly above), when the concave portion (Z2) has a long side and a short side, the short side is referred to as a width.

Ratio of the maximum height difference and the average width of the single recess (Z2) [maximum height difference / average width] (in the recess (Z2) 22 shown in FIG. 5A, “H ₂ the / _{L 2} refers to "), preferably 1 / 500-100 / 1, more preferably 3 / 400-70 / 3, more preferably 1/60 to 10/1.

  In addition, the some recessed part (Z2) which has on the surface (2) of a resin layer bears the auxiliary | assistant role which deform | transforms a resin layer, when the surface (1) of a resin layer is pressed against a to-be-adhered body. That is, by having a plurality of recesses (Z2) on the surface (2) of the resin layer, when the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is attached to the adherend, the recesses on the surface (1) (Z1) can be deformed to such an extent that it can serve as an air discharge passage that can release an air pocket generated during sticking to the adherend to the outside.

<Requirement (IIb)>
As for the adhesive sheet of this invention, 95% or more of several recessed part (Z2) which exists in the area | region (P2) on the surface (2) has a mutually different shape as said requirement (IIb). As described above, the plurality of recesses (Z2) are not formed using a release material or the like on which an emboss pattern is applied.
In the pressure-sensitive adhesive sheet of the present invention, 95% or more of the plurality of recesses (Z2) existing on the surface (2) of the resin layer have shapes different from each other, which improves the mobility of the resin layer. This contributes to improved air bleedability in conjunction with a plurality of recesses (Z1) that appear or exist on the surface (1) of the resin layer.

  Note that in the pressure-sensitive adhesive sheet of one embodiment of the present invention, the ratio of the plurality of recesses (Z2) having different shapes existing in the region (P2) on the surface (2) of the resin layer is the region (P2) Is preferably 98% or more, and more preferably 100%, with respect to the total number (100%) of the recesses present in.

  In the present invention, the determination as to whether or not the requirement (IIb) is satisfied is the same as described in the requirement (IIa) regarding the recess (Z1).

<Requirement (IIIb)>
The pressure-sensitive adhesive sheet of one embodiment of the present invention has one concave portion (Z2) in a region (Q2) surrounded by a square with a side of 1 mm arbitrarily selected on the surface (2) as required (IIIb). It is preferable to exist above.
When one or more recesses (Z2) are present in the region (Q2), it is possible to further improve the mobility of the resin layer.
From the above viewpoint, the number of the concave portions (Z2) present in the region (Q2) is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. On the other hand, the appearance and adhesive properties are good. From the standpoint of maintaining the thickness, it is preferably 1000 or less, more preferably 500 or less.

Moreover, when the surface (2) of the resin layer of the adhesive sheet of this invention has adhesiveness, it is also possible to affix the surface (2) to a to-be-adhered body. In such a case, the plurality of recesses (Z2) on the surface (2) serve as an air discharge passage for escaping an “air pool” generated when the pressure-sensitive adhesive sheet is attached to the adherend. Bear.
In the pressure-sensitive adhesive sheet having the adhesiveness on the surface (2) of the resin layer, a region (Q2) surrounded by a square with a side of 1 mm arbitrarily selected on the surface (2) from the viewpoint of improving air bleeding. It is preferable that one or more of the recesses (Z2) existing in () extend to any side of a square with a side of 1 mm, which is the boundary line of the region (Q2).
The number of intersections between any one side of a square having a side of 1 mm that is the boundary line between the recess (Z2) and the region (Q2) is preferably 1 or more, more preferably 2 or more, More preferably, the number is 3 or more.

Moreover, in the adhesive sheet in which the surface (2) of the resin layer is adhesive, one or more of the recesses (Z2) existing in the region (Q2) on the surface (2) are present from the viewpoint of improving air bleeding. Preferably, the region (Q2) has a shape extending continuously into one or more other regions (Q2 ′) surrounded by a 1 mm square adjacent to the region (Q2), and two or more other regions (Q2 ′). ) Is more preferable to have a shape that continuously extends to the inside, and still more preferably a shape that continuously extends to three or more other regions (Q2 ′).
Further, the recess (Z2) present in the region (Q2) on the surface (2) of the resin layer is not only one or more other regions (Q2 ′) adjacent to the region (Q2) but also other regions. It is preferable that the shape further extends continuously to the region (Q2 ″) other than the region (Q2 ′) adjacent to (Q2 ′).

<Requirement (IVb)>
As for the adhesive sheet of 1 aspect of this invention, it is preferable that a several recessed part (Z2) exists irregularly on the surface (2) of a resin layer as said requirement (IVa).
In the present invention, the definition that “the plurality of recesses (Z2) are irregularly present” is irregular (random) where the positions of the plurality of recesses (Z2) do not have the same repeating pattern. This means a state (a state in which a plurality of recesses (Z1) appear or has no periodicity at positions where it exists), and is the same as the requirement (IV) of the above-described recess (Z1).
Since the plurality of recesses (Z2) are irregularly present on the surface (2) of the resin layer, more recesses (Z1) appear on the surface (1), and the plurality of recesses on the surface (1). In conjunction with (Z1), the pressure-sensitive adhesive sheet can be further improved in air bleeding.
In the present invention, the determination as to whether or not the requirement (IVb) is satisfied is the same as the description of the requirement (IVa) regarding the recess (Z1).

<Requirement (Vb)>
As for the adhesive sheet of 1 aspect of this invention, it is preferable that the surface shape except a some recessed part (Z2) is indeterminate in the surface (2) of a resin layer as the said requirement (Vb).
When the surface (2) has adhesiveness and the pressure-sensitive adhesive sheet is used as a double-sided pressure-sensitive adhesive sheet, the surface is a “sticking surface” to the adherend.
In addition, the meaning of the word “the shape of the surface is indefinite” and the determination method of “whether the shape of the surface is indeterminate” are based on the requirement (Va) for the recess (Z1). Same as described.

Hereinafter, each structure of the adhesive sheet of this invention is demonstrated.
〔Base material〕
The substrate used in one embodiment of the present invention is not particularly limited, and examples thereof include a paper substrate, a resin film or sheet, a substrate obtained by laminating a paper substrate with a resin, and the like. It can select suitably according to the use of a sheet.
Examples of the paper constituting the paper substrate include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfuric acid paper, glassine paper and the like.
Examples of the resin constituting the resin film or sheet include polyolefin resins such as polyethylene and polypropylene; vinyl such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer. Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; urethane resin such as polyurethane and acrylic modified polyurethane; polymethylpentene; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene sulfide; Polyimide resins such as polyetherimide and polyimide; Polyamide resins, acrylic resins, fluorine-based resins.
Examples of the base material obtained by laminating a paper base material with a resin include laminated paper obtained by laminating the paper base material with a thermoplastic resin such as polyethylene.

Among these substrates, a resin film or sheet is preferable, a film or sheet made of a polyester resin is more preferable, and a film or sheet made of polyethylene terephthalate (PET) is still more preferable.
In addition, when the pressure-sensitive adhesive sheet of the present invention is used for an application requiring heat resistance, a film or sheet composed of a resin selected from polyethylene naphthalate and a polyimide resin is preferable, and an application requiring weather resistance. When used in a film, a film or sheet composed of a resin selected from polyvinyl chloride, polyvinylidene chloride, acrylic resin, and fluororesin is preferable.

Although the thickness of a base material is suitably set according to the use of the adhesive sheet of this invention, from a viewpoint of handleability and economical efficiency, Preferably it is 5-1000 micrometers, More preferably, it is 10-500 micrometers, More preferably, 12- The thickness is 250 μm, more preferably 15 to 150 μm.
In addition, the base material may further contain various additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.

In addition, the base material used in one embodiment of the present invention is preferably a non-breathable base material from the viewpoint of improving the blister resistance of the obtained pressure-sensitive adhesive sheet, and specifically, the surface of the above-described resin film or sheet. A substrate having a metal layer thereon is preferred.
Examples of the metal formed by the metal layer include metals having metallic luster such as aluminum, tin, chromium, and titanium.
As a method for forming the metal layer, for example, a method of depositing the metal by a PVD method such as vacuum deposition, sputtering, or ion plating, or a metal foil made of the metal is attached using a general adhesive. The method etc. are mentioned, The method of vapor-depositing the said metal by PVD method is preferable.

Furthermore, when using a resin film or sheet as a base material, from the viewpoint of improving the adhesion with the resin layer laminated on these resin films or sheets, the surface of the resin film or sheet is oxidized or uneven. Surface treatment by a method or the like, or primer treatment may be performed.
Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone, and ultraviolet irradiation treatment. Examples of the unevenness method include sand blast method and solvent treatment method. Etc.

[Release materials (R1), (R2)]
As the release material (R1) and the release material (R2) used in one embodiment of the present invention, a release sheet subjected to a double-sided release process, a release sheet subjected to a single-sided release process, or the like is used. And the like coated with a release agent. In addition, the said peeling process surface does not have uneven | corrugated shape, and the peeling material (for example, the peeling material in which the embossing pattern is not given) which is flat is preferable.
In particular, in one embodiment of the present invention, it is preferable that the surface of the release material (R1) that is in contact with the surface (1) of the resin layer is a release treatment surface on which an uneven shape is not formed. More preferably, the surface is a release treatment surface that is not provided with an emboss pattern.
Examples of the base material for the release material include the above-described paper base material, resin film or sheet used as the base material included in the pressure-sensitive adhesive sheet of one embodiment of the present invention, and a base material obtained by laminating a paper base material with a resin. It is done.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
Although there is no restriction | limiting in particular in the thickness of a peeling material, Preferably it is 10-200 micrometers, More preferably, it is 25-150 micrometers, More preferably, it is 35-80 micrometers.

[Resin layer]
The resin layer of the pressure-sensitive adhesive sheet of the present invention includes a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles.
Moreover, although the surface (1) of the said resin layer in the side in which the peeling material (R1) was provided has adhesiveness, the adhesive sheet of this invention was provided with the base material or the peeling material (R2). The surface (2) of the resin layer on the side may also have adhesiveness.

As the resin layer, a layer (X1) mainly containing the resin part (X) and a layer containing 15% by mass or more of the particle part (Y) from the release material (R1) side, such as the adhesive sheet 1a of FIG. A configuration of a layer formed by forming a multilayer structure in which (Y1) and a layer (X2) mainly including the resin portion (X) are laminated in this order can be given.
Note that the structure of the multilayer structure described above is a mixed structure in which the boundary between the layer (X1) and the layer (Y1) and / or the boundary between the layer (Y1) and the layer (X2) cannot be determined. There may be.

The layer (X1) and the layer (X2) are layers mainly including the resin portion (X), but may include a particle portion (Y). However, the content of the particle part (Y) in the layer (X1) and the layer (X2) is each independently 15 masses with respect to the total mass (100 mass%) of the layer (X1) or the layer (X2). % And less than the content of the resin constituting the resin part (X).
The layer (X1) and the layer (X2) may further have a void portion (Z) described later in addition to the resin portion (X) and the particle portion (Y).

As content of resin in a layer (X1) and a layer (X2), it is 50-100 mass% normally with respect to the total mass (100 mass%) of a layer (X1) or a layer (X2), respectively. Preferably it is 65-100 mass%, More preferably, it is 75-100 mass%, More preferably, it is 85-100 mass%, More preferably, it is 90-100 mass%.
In the present invention, the “content of the resin in the layer (X1) and the layer (X2)” is the total amount (100% by mass (100% by mass)) of the resin composition that is a material for forming the layer (X1) or the layer (X2). However, it can be regarded as the content of the resin in a)) except for the dilution solvent.

Moreover, as content of the microparticles | fine-particles which comprise the particle | grain part (Y) in a layer (X1) and a layer (X2), it is respectively independently in the total mass (100 mass%) of a layer (X1) or a layer (X2). On the other hand, although it is less than 15 mass%, Preferably it is 0-13 mass%, More preferably, it is 0-10 mass%, More preferably, it is 0-5 mass%, More preferably, it is 0 mass%.
In the present invention, “the content of fine particles in the layer (X1) and the layer (X2)” refers to the total amount (100 mass% (100% by mass ( However, it can also be regarded as the content of fine particles in a)) excluding a diluting solvent.
In addition, the layer (X1) and the layer (X2) are preferably formed from compositions (x1) and (x2) containing a resin as a main component described later.

The layer (Y1) containing 15% by mass or more of the particle part (Y) may be a layer composed only of the particle part (Y), or may be a layer containing the resin part (X) together with the particle part (Y). Moreover, you may have the space | gap part (Z) mentioned later further.
The content of the fine particles constituting the particle portion (Y) in the layer (Y1) is 15% by mass or more with respect to the total mass (100% by mass) of the layer (Y1), preferably 20 to 100. The mass% is more preferably 25 to 90 mass%, still more preferably 30 to 85 mass%, and still more preferably 35 to 80 mass%.
In the present invention, “the content of the fine particles in the layer (Y1)” means the fine particles in the total amount (100% by mass (excluding the diluting solvent)) of the composition that is a forming material of the layer (Y1). It can also be regarded as the content of.
Moreover, as content of the resin in a layer (Y1), it is 1-85 mass% normally with respect to the total mass (100 mass%) of a layer (Y1), Preferably it is 5-80 mass%, More preferably, it is 10 It is -75 mass%, More preferably, it is 20-70 mass%, More preferably, it is 25-65 mass%.
In addition, in this invention, "content of the resin in a layer (Y1)" is resin in the whole quantity (100 mass% (however, except a dilution solvent)) of the composition which is the formation material of the said layer (Y1). It can also be regarded as the content of.
Moreover, it is preferable that the said layer (Y1) is a layer formed from the composition (y) which contains the below-mentioned microparticles | fine-particles 15 mass% or more.

It is preferable that the resin layer which the adhesive sheet of 1 aspect of this invention has has a space | gap part (Z) further besides resin part (X) and particle | grain part (Y). By having a void portion (Z) in the resin layer, the blister resistance of the pressure-sensitive adhesive sheet can be improved.
The void portion (Z) includes voids that exist between the fine particles, and voids that exist in the secondary particles when the fine particles are secondary particles.
When the resin layer has a multilayer structure, the resin portion (X) flows into the void portion (Z) even if the void portion (Z) exists immediately after the formation of the resin layer or immediately after the formation. In some cases, the voids disappear and the resin layer has no void portion (Z).
However, even when the void portion (Z) that has been present in the resin layer for a period of time disappears in this manner, the resin layer included in the pressure-sensitive adhesive sheet according to one embodiment of the present invention has a concave portion on the surface (1). Therefore, it can be excellent in air bleeding and blister resistance.

In addition, the shear storage elastic modulus at 100 ° C. of the resin layer included in the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 9.0 × 10 ³ Pa or more from the viewpoint of improving the air release property and blister resistance of the pressure-sensitive adhesive sheet. More preferably, it is 1.0 × 10 ⁴ Pa or more, and further preferably 2.0 × 10 ⁴ Pa or more.
In the present invention, the shear storage modulus at 100 ° C. of the resin layer is measured by measuring at a frequency of 1 Hz using a viscoelasticity measuring device (for example, device name “DYNAMIC ANALYZER RDA II” manufactured by Rheometrics). Means the value.

  The thickness of the resin layer is preferably 1 to 300 μm, more preferably 5 to 150 μm, and still more preferably 10 to 75 μm.

The adhesive strength on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 0.5 N / 25 mm or more, more preferably 2.0 N / 25 mm or more, more preferably 3.0 N / 25 mm or more. More preferably, it is 4.0 N / 25 mm or more, and still more preferably 7.0 N / 25 mm or more.
Moreover, when the surface (2) of the resin layer also has adhesiveness, it is preferable that the adhesive force in the surface (2) also belongs to said range.
In addition, the value of the said adhesive force of an adhesive sheet means the value measured by the method as described in an Example.

<Resin part (X)>
The resin part (X) constituting the resin layer contains a resin as a main component.
In the present invention, the resin portion (X) is a portion containing components other than the fine particles contained in the resin layer, and is distinguished from the particle portion (Y) in that respect.
The resin part (X) contains a resin as a main component and may contain a crosslinking agent or a general-purpose additive in addition to the resin.

In the pressure-sensitive adhesive sheet of the present invention, the elastic modulus at 23 ° C. of the resin portion (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa, preferably 1.0 × 10. ^{It is} 4-1.0 * 10 < ⁸ > Pa, More preferably, it is 5.0 * 10 < ⁴ > -1.0 * 10 < ⁷ > Pa, More preferably, it is 1.0 * 10 < ⁵ > -1.0 * 10 < ⁶ > Pa.
When the elastic modulus of the resin portion (X) on the surface (1) is within the above range, the recess (Z1) is likely to appear when the release material (R1) is removed. Further, since the resin portion (X) in the vicinity of the surface (1) is easily deformed moderately, an air pocket generated between the surface (1) and the adherend when the surface (1) is attached to the adherend. Due to this pressure, the recess (Z1) is easily deformed. As a result, the air reservoir can be removed to the outside through the recess (Z1) despite the relatively shallow recess (Z1).
In addition, when the said elasticity modulus is less than 1.0 * 10 < ³ > Pa, when removing a peeling material (R1), it will become difficult to make a recessed part (Z1) appear. Moreover, the shape maintenance property of a recessed part (Z1) is inferior, it is difficult to remove an air pocket outside through a recessed part (Z1), and the air bleeding property of an adhesive sheet falls.
On the other hand, when the elastic modulus exceeds 8.0 × 10 ⁸ Pa, it is difficult to cause the recess (Z1) to appear when the release material (R1) is removed. Further, the recess (Z1) is not easily deformed to such an extent that the air pocket can be removed to the outside, and the air release property of the adhesive sheet is lowered.

  In the present invention, the value of the elastic modulus at 23 ° C. of the resin portion (X) on the surface (1) is “J. Vac. Soc. Jpn. Vol. 56, No. 7, 2013 p258 Ken Nakajima It is a value measured according to the elastic modulus measurement method described in `` Development of a method for quantitative evaluation of elastic modulus of soft materials using a force microscope '' and specifically means a value measured by the method described in the examples. To do.

The resin content in the resin part (X) is usually 40% by mass or more, preferably 50% by mass or more, more preferably 65% by mass or more, based on the total amount (100% by mass) of the resin part (X). More preferably, it is 75 mass% or more, More preferably, it is 85 mass% or more, More preferably, it is 90 mass% or more, Preferably it is 100 mass% or less, More preferably, it is 99.9 mass% or less.
In the present invention, the value of the content of the resin in the resin composition that is the material for forming the resin portion (X) can also be regarded as the “content of the resin in the resin portion (X)”.

The resin contained in the resin portion (X) preferably contains a tacky resin from the viewpoint of developing tackiness on the surface (1) of the resin layer to be formed.
In particular, as in the adhesive sheet 1a in FIG. 1A, the resin layer is a multilayer in which the layer (X1), the layer (Y1), and the layer (X2) are laminated in this order from the release material (R1) side. In the case of having a structure, from the above viewpoint, at least the layer (X1) preferably contains an adhesive resin.

Examples of the adhesive resin include acrylic resins, rubber resins, urethane resins, and silicone resins.
Among these adhesive resins, the adhesive properties and weather resistance are good, and when the release material (R1) is removed, the surface (1) of the resin layer satisfies the above requirements (Ia) to (IIa). From the viewpoint of facilitating the appearance of the recess (Z1), it is preferable to include at least one of an acrylic resin and a rubber resin, and the surface (2) of the resin layer satisfies the above requirements (Ib) to (IIb) From the viewpoint of easily forming the plurality of recesses (Z2), it is more preferable to include an acrylic resin.
The content of the adhesive resin selected from the acrylic resin and the rubber resin is preferably 25 to 100% by mass, more preferably based on the total amount (100% by mass) of the resin contained in the resin part (X). 50-100 mass%, More preferably, it is 70-100 mass%, More preferably, it is 80-100 mass%, More preferably, it is 100 mass%.

In addition, when the release material (R1) is removed, a point of making the plurality of recesses (Z1) satisfying the above requirements (Ia) to (IIa) easily appear on the surface (1) of the resin layer, and the resin layer From the viewpoint of facilitating formation of a plurality of recesses (Z2) satisfying the above-mentioned requirements (Ib) to (IIb) on the surface (2) of the resin, the resin part (X) preferably contains a resin having a functional group, It is more preferable to include an acrylic resin having a functional group.
In particular, as in the adhesive sheet 1a in FIG. 1A, the resin layer is a multilayer in which the layer (X1), the layer (Y1), and the layer (X2) are laminated in this order from the release material (R1) side. In the case of having a structure, from the above viewpoint, at least the layer (Y1) preferably contains a resin having a functional group.
The functional group is a group that is a starting point of crosslinking with a crosslinking agent, and examples thereof include a hydroxy group, a carboxy group, an epoxy group, an amino group, a cyano group, a keto group, and an alkoxysilyl group. preferable.

In addition, it is preferable that resin part (X) contains a crosslinking agent further with resin which has the said functional group. In particular, when the resin layer has the multilayer structure, at least the layer (Y1) preferably contains a crosslinking agent together with the resin having the functional group.
Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.

  Examples of the isocyanate-based crosslinking agent include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; In addition, biuret bodies, isocyanurate bodies of these compounds, and adduct bodies that are a reaction product of low molecular active hydrogen-containing compounds (ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc.); Is mentioned.

  Examples of the epoxy-based cross-linking agent include ethylene glycol glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, Examples include 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like.

  Examples of the aziridine-based crosslinking agent include diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinyl. Propionate, toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1- (2-methylaziridine), tris-1- (2-methylaziridine) phosphine, And trimethylolpropane tri-β- (2-methylaziridine) propionate.

Examples of the metal chelate-based crosslinking agent include chelate compounds whose metal atoms are aluminum, zirconium, titanium, zinc, iron, tin, and the like, and an aluminum chelate-based crosslinking agent is preferable.
Examples of the aluminum chelate-based crosslinking agent include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bis oleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopropoxy aluminum monolauryl acetoacetate, Examples include isopropoxyaluminum monostearyl acetoacetate and diisopropoxyaluminum monoisostearyl acetoacetate.

In addition, you may use these crosslinking agents individually or in combination of 2 or more types.
Among these, when removing the release material (R1), a viewpoint of easily causing a plurality of recesses (Z1) satisfying the above requirements (Ia) to (IIa) on the surface (1) of the resin layer, and From the viewpoint of facilitating formation of a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) on the surface (2) of the resin layer, the resin portion (X) is composed of a metal chelate crosslinking agent and an epoxy crosslinking. It is preferable to include one or more selected from agents, more preferably to include a metal chelate crosslinking agent, and even more preferably to include an aluminum chelate crosslinking agent.

  The content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 0.3 to 7.0 with respect to 100 parts by mass of the resin having a functional group. Part by mass.

In addition, from the viewpoint of improving the shape maintainability of the recess (Z1) on the surface (1) and the recess (Z2) on the surface (2) of the resin layer, the resin portion (X) contains a metal chelate crosslinking agent and It is preferable that an epoxy type crosslinking agent is included together.
When the resin part (X) contains both a metal chelate crosslinking agent and an epoxy crosslinking agent, from the above viewpoint, the content ratio of the metal chelate crosslinking agent and the epoxy crosslinking agent in the resin part (X) [metal chelate system The cross-linking agent / epoxy-based cross-linking agent] is preferably 10/90 to 99.5 / 0.5, more preferably 50/50 to 99.0 / 1.0, and still more preferably 65/35 by mass ratio. To 98.5 / 1.5, more preferably 75/25 to 98.0 / 2.0.

Moreover, the resin part (X) may contain a general-purpose additive.
General-purpose additives include, for example, tackifiers, antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators, ultraviolet absorbers, and the like.
These general-purpose additives may be used alone or in combination of two or more.
When these general-purpose additives are contained in the resin part (X), the content of each general-purpose additive is preferably 0.0001 to 60 parts by mass, more preferably 0.001 to 100 parts by mass of the resin. 001 to 50 parts by mass.

The said resin contained in resin part (X) may be only 1 type, and may be used in combination of 2 or more type.
The material for forming the resin part (X) of the resin layer of the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive containing a pressure-sensitive adhesive resin having a functional group, and an acrylic pressure-sensitive adhesive containing an acrylic resin having a functional group. More preferred is a rubber-based pressure-sensitive adhesive containing an agent or a rubber-based resin.
Hereinafter, an acrylic pressure-sensitive adhesive and a rubber-based pressure-sensitive adhesive that are suitable as the forming material of the resin portion (X) will be described.

(Acrylic adhesive)
The acrylic pressure-sensitive adhesive that is a material for forming the resin portion (X) may be either a solvent type or an emulsion type. The acrylic pressure-sensitive adhesive preferably contains an acrylic resin (A) having a functional group (hereinafter also simply referred to as “acrylic resin (A)”) and a crosslinking agent (B).
Examples of the acrylic resin (A) contained in the acrylic pressure-sensitive adhesive include a polymer having a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group and a cyclic structure ( Examples thereof include a polymer having a structural unit derived from (meth) acrylate.
The mass average molecular weight (Mw) of the acrylic resin (A) is preferably 50,000 to 1,500,000, more preferably 150,000 to 1,300,000, still more preferably 250,000 to 1,100,000, still more preferably 350,000 to 90. Ten thousand.

As the acrylic resin (A), a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) having an alkyl group having 1 to 18 carbon atoms (hereinafter also referred to as “monomer (a1 ′)”), And an acrylic copolymer (A1) having a structural unit (a2) derived from the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”). More preferably, it is a combination (A1).
The content of the acrylic copolymer (A1) is preferably 50 to 100% by mass, more preferably 70 to 100%, based on the total amount (100% by mass) of the acrylic resin (A) in the acrylic adhesive. It is 80 mass%, More preferably, it is 80-100 mass%, More preferably, it is 90-100 mass%.
In addition, the form of copolymerization of the acrylic copolymer (A1) is not particularly limited, and may be any of a block copolymer, a random copolymer, and a graft copolymer.

As carbon number of the alkyl group which a monomer (a1 ') has, from a viewpoint of the improvement of an adhesive characteristic, More preferably, it is 4-12, More preferably, it is 4-8, More preferably, it is 4-6.
Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate.
Among these, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.

  The content of the structural unit (a1) is preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, with respect to the total structural unit (100% by mass) of the acrylic copolymer (A1). More preferably, it is 70-95 mass%, More preferably, it is 80-93 mass%.

Examples of the monomer (a2 ′) include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. .
Among these, a carboxy group-containing monomer is more preferable.
Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and (meth) acrylic acid is preferred.

  The content of the structural unit (a2) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight, based on all the structural units (100% by weight) of the acrylic copolymer (A1). More preferably, it is 5-30 mass%, More preferably, it is 7-20 mass%.

The acrylic copolymer (A1) may have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
Examples of the other monomer (a3 ′) include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyl. Examples thereof include (meth) acrylate having a cyclic structure such as oxyethyl (meth) acrylate and imide (meth) acrylate, vinyl acetate, acrylonitrile, and styrene.

The content of the structural unit (a3) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and still more preferably based on the total structural unit (100% by mass) of the acrylic copolymer (A1). Is 0 to 10% by mass, more preferably 0 to 5% by mass.
In addition, you may use the above-mentioned monomer (a1 ')-(a3') individually or in combination of 2 or more types.

  The method for synthesizing the acrylic copolymer (A1) component is not particularly limited. For example, the raw material monomer is dissolved in a solvent and solution polymerization is performed in the presence of a polymerization initiator, a chain transfer agent, or the like. In the presence of a method, an emulsifier, a polymerization initiator, a chain transfer agent, a dispersant, and the like, it is produced by emulsion polymerization in an aqueous system using raw material monomers.

Examples of the crosslinking agent (B) contained in the acrylic pressure-sensitive adhesive include those described above. From the viewpoint of improving the pressure-sensitive adhesive properties, the surface of the resin layer (1) when the release material (R1) is removed. ) To make the plurality of recesses (Z1) satisfying the above requirements (Ia) to (IIa) easily appear, and a plurality satisfying the above requirements (Ib) to (IIb) on the surface (2) of the resin layer From the viewpoint of facilitating the formation of the recess (Z2), it is preferable to include one or more selected from a metal chelate crosslinking agent and an epoxy crosslinking agent, more preferably a metal chelate crosslinking agent, and an aluminum chelate system. More preferably, it contains a crosslinking agent.
From the viewpoint of improving the shape maintaining property of the recesses (Z1) on the surface (1) and the recesses (Z2) on the surface (2) of the resin layer, the crosslinker (B) may be a metal chelate crosslinker. And an epoxy-based crosslinking agent are preferably included.

  The content of the crosslinking agent (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic resin (A) in the acrylic adhesive. More preferably, it is 0.3 to 7.0 parts by mass.

  When a metal chelate crosslinking agent and an epoxy crosslinking agent are used in combination, the content ratio of the metal chelate crosslinking agent and the epoxy crosslinking agent [metal chelate crosslinking agent / epoxy crosslinking agent] is preferably a mass ratio, preferably 10/90 to 99.5 / 0.5, more preferably 50/50 to 99.0 / 1.0, still more preferably 65/35 to 98.5 / 1.5, still more preferably 75/25 98.0 / 2.0.

  The acrylic pressure-sensitive adhesive used in one embodiment of the present invention may contain a general-purpose additive as long as the effects of the present invention are not impaired. Examples of the general-purpose additive include those described above, and the content of the general-purpose additive is also as described above.

In the acrylic pressure-sensitive adhesive used in one embodiment of the present invention, a pressure-sensitive resin other than the acrylic resin (A) (for example, urethane-based resin, rubber-based resin, silicone-based resin, etc.) within a range that does not impair the effects of the present invention. ) May be contained.
The content of the acrylic resin (A) in the acrylic pressure-sensitive adhesive is preferably 50 to 100% by mass, more preferably 70%, based on the total amount (100% by mass) of the adhesive resin contained in the acrylic pressure-sensitive adhesive. -100 mass%, More preferably, it is 80-100 mass%, More preferably, it is 100 mass%.

(Rubber adhesive)
As a material for forming the resin portion (X) of the present invention, a rubber-based adhesive containing a rubber-based resin may be used.
The rubber-based pressure-sensitive adhesive is suitable as a material for forming the resin portion (X) on the surface (1) side from the viewpoint of adjusting the elastic modulus of the resin portion (X) on the surface (1) of the resin layer to the above range. is there.

As the rubber resin, for example, synthetic rubber such as polyisobutylene resin and polybutene resin, or natural rubber can be used.
The weight average molecular weight of the rubber-based resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, and still more preferably, from the viewpoint of improving the adhesive strength and the wettability with respect to the adherend and the solubility with respect to the solvent. It is 50,000 to 800,000, more preferably 70,000 to 600,000.

The content of the rubber-based resin with respect to the total amount (100% by mass) of the rubber-based adhesive is preferably 30 to 100% by mass, more preferably 40 to 90% by mass, and still more preferably 45 from the viewpoint of improving the adhesive strength. It is -80 mass%, More preferably, it is 50-70 mass%.
The rubber-based adhesive may contain a tackifier resin and general-purpose additives (light stabilizer, antioxidant, ultraviolet absorber, resin stabilizer, pigment, extender, softener, etc.) together with the rubber resin. Good.

<Polyisobutylene resin>
Of the rubber resins, polyisobutylene resins are preferable.
In the present invention, the structure of the polyisobutylene resin is a resin having a polyisobutylene skeleton in the main chain or side chain, and specifically, a resin having the following structural unit (a).

Examples of the polyisobutylene resin include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers And halogenated butyl rubber obtained by bromination or chlorination.
In addition, when polyisobutylene resin is a copolymer, the structural unit derived from isobutylene shall be contained most among all the structural units.
The content of the structural unit derived from isobutylene in the polyisobutylene resin is preferably 80 to 100% by mass, more preferably 90 to 100% by mass with respect to all the structural units (100% by mass) of the polyisobutylene resin. %, More preferably 95 to 100% by mass, and still more preferably 100% by mass.
These polyisobutylene resins may be used alone or in combination of two or more.

The polyisobutylene resin used in one embodiment of the present invention includes a polyisobutylene resin (α) having a mass average molecular weight of 2.7 to 1,200,000 and a polyisobutylene resin (β) having a mass average molecular weight of 5 to 250,000. It is preferable to include both.
By including a high molecular weight polyisobutylene resin (α) in the rubber-based adhesive, the durability and weather resistance of the resin layer formed from the rubber-based adhesive can be improved and the adhesive strength can be improved. it can.
In addition, the low molecular weight polyisobutylene resin (β) is well compatible with the PIB resin (α) in the rubber-based pressure-sensitive adhesive and plays a role in appropriately plasticizing the PIB resin (α). Thereby, the wettability with respect to the to-be-adhered body of the resin layer formed is improved, an adhesive physical property, a softness | flexibility, etc. are improved, and it contributes also to the improvement of an air release property. In addition, you may use said polyisobutylene-type resin ((alpha)) and ((beta)) individually or in combination of 2 or more types, respectively.

The mass average molecular weight of the polyisobutylene resin (α) is preferably 270,000 to 1,200,000, more preferably 290,000 to 1,000,000, still more preferably 31 to 800,000, still more preferably 320,000 to 40,000. Ten thousand.
If the mass average molecular weight is 270,000 or more, the cohesive force of the prepared pressure-sensitive adhesive can be sufficiently improved, and the concern about contamination of the adherend can be eliminated.
On the other hand, if the mass average molecular weight is 1,200,000 or less, the cohesive force of the prepared pressure-sensitive adhesive becomes too high, and thus the adverse effect of flexibility and fluidity can be avoided, and a resin formed from the pressure-sensitive adhesive The wetting of the layer with the adherend can be improved. Moreover, when preparing an adhesive, the solubility with respect to a solvent can also be made favorable.

The mass average molecular weight of the polyisobutylene resin (β) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 180,000 to 21. Ten thousand.
If the mass average molecular weight is 50,000 or more, the polyisobutylene resin (β) in the resin layer to be formed is separated as a low molecular component and can be prevented from being transferred to the adherend and contaminated. it can. Moreover, the outgas generation amount under high temperature can be reduced.
On the other hand, when the mass average molecular weight is 250,000 or less, the polyisobutylene resin (α) can be sufficiently plasticized, and the wettability of the surface of the formed resin layer can be improved.

  The content ratio of the polyisobutylene resin (β) to 100 parts by mass of the polyisobutylene resin (α) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, More preferably, it is 8-20 mass parts.

  The content of the polyisobutylene resin with respect to the total amount (100% by mass) of the rubber-based adhesive is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably from the viewpoint of improving the adhesive strength. It is 45-80 mass%, More preferably, it is 50-70 mass%.

<Tackifying resin>
The rubber-based pressure-sensitive adhesive used in the present invention preferably further contains a tackifier resin from the viewpoint of improving the tackiness.
The tackifying resin can be mixed with a rubber-based resin, and has a function of improving the adhesive performance of the rubber-based resin, and has a mass average molecular weight of less than 20,000 (preferably 100 to 10,000). In the oligomer region.

Examples of tackifier resins include rosin resins, rosin phenol resins, and ester compounds thereof; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, terpene phenol resins, aromatic modified terpenes Terpene resins such as pentene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; copolymerization of C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 petroleum resin obtained and hydrogenated petroleum resin of this C5 petroleum resin; C9 fractions such as indene, vinyltoluene, α-methylstyrene, β-methylstyrene produced by thermal decomposition of petroleum naphtha are copolymerized And a C9 petroleum resin obtained by hydrogenation and a hydrogenated petroleum resin of the C9 petroleum resin.
Among these, at least one selected from rosin resins, hydrogenated rosin resins, terpene resins, hydrogenated terpene resins, and hydrogenated petroleum resins is preferable, from the viewpoint of high compatibility with polyisobutylene resins, Hydrogenated petroleum resin is more preferable.
In addition, you may use these tackifier resin individually or in combination of 2 or more types.

The softening point of the tackifier resin is preferably 60 to 170 ° C, more preferably 75 to 150 ° C, still more preferably 85 to 140 ° C, and still more preferably 90 to 130 ° C, from the viewpoint of improving the tackiness.
The value of the softening point of the tackifier resin is a value measured in accordance with JIS K2531.

  The content of the tackifying resin is preferably 5 to 60% by mass and more preferably 10 to 50% by mass with respect to the total amount (100% by mass) of the rubber-based adhesive.

<Particle part (Y)>
The particle portion (Y) constituting the resin layer is made of fine particles.
As the average particle diameter of the fine particles, a plurality of sheets satisfying the above requirements (Ia) to (IIa) on the surface (1) of the resin layer to be formed, from the viewpoint of improving the air bleeding property and blister resistance of the pressure-sensitive adhesive sheet From the viewpoint of facilitating the appearance or formation of the recess (Z1) and from the viewpoint of facilitating the formation of the plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) on the surface (2), preferably It is 0.01-100 micrometers, More preferably, it is 0.05-25 micrometers, More preferably, it is 0.1-10 micrometers.

The fine particles used in one embodiment of the present invention are not particularly limited, and include inorganic particles such as silica particles, metal oxide particles, barium sulfate, calcium carbonate, magnesium carbonate, glass beads, smectite, and organic particles such as acrylic beads. Can be mentioned.
Among these fine particles, one or more selected from silica particles, metal oxide particles, and smectites are preferable, and silica particles are more preferable.

The silica particles used in one embodiment of the present invention may be either dry silica or wet silica.
In addition, the silica particles used in one embodiment of the present invention include organic modified silica surface-modified with an organic compound having a reactive functional group, inorganic modified silica surface-treated with an inorganic compound such as sodium aluminate or sodium hydroxide In addition, organic-inorganic modified silica surface-treated with these organic compounds and inorganic compounds, organic-inorganic modified silica surface-treated with an organic-inorganic hybrid material such as a silane coupling agent, and the like may be used.
In addition, the mixture which consists of 2 or more types may be sufficient as these silica particles.

The mass concentration of silica in the silica particles is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount (100% by mass) of the silica particles. .
Moreover, the volume average secondary particle diameter of the silica particles used in one embodiment of the present invention is the above-mentioned on the surface (1) of the resin layer to be formed, from the viewpoint of improving the air bleeding property and blister resistance of the pressure-sensitive adhesive sheet. From the viewpoint of facilitating the appearance or formation of a plurality of recesses (Z1) satisfying the requirements (Ia) to (IIa), and a plurality of recesses satisfying the above requirements (Ib) to (IIb) on the surface (2) ( From the viewpoint of facilitating formation of Z2), it is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and still more preferably 1.5 to 5 μm.
In the present invention, the value of the volume average secondary particle diameter of the silica particles is a value obtained by measuring the particle size distribution by a Coulter counter method using a multisizer three machine or the like.

  Examples of the metal oxide particles include particles made of metal oxide selected from titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof. The sol particle | grains which consist of these metal oxides are also included.

  Examples of the smectite include montmorillonite, beidellite, hectorite, saponite, stevensite, nontronite, and soconite.

The mass retention after heating the resin layer of the pressure-sensitive adhesive sheet of one embodiment of the present invention at 800 ° C. for 30 minutes is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and still more preferably 7 to 70%. It is 9 mass%, More preferably, it is 9-60 mass%.
The mass retention rate can be regarded as indicating the content (% by mass) of fine particles contained in the resin layer.
If the said mass retention is 3 mass% or more, it can become an adhesive sheet excellent in air bleeding property and blister resistance. Moreover, at the time of manufacture of the pressure-sensitive adhesive sheet of the present invention, a plurality of recesses (Z1) satisfying the above requirements (Ia) to (IIa) are likely to appear or be formed on the surface (1) of the formed resin layer. Moreover, on the surface (2), a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) are easily formed.
On the other hand, when the mass retention is 90% by mass or less, the resin layer has high film strength and can be a pressure-sensitive adhesive sheet having excellent water resistance and chemical resistance.

[Method for producing adhesive sheet]
Next, the manufacturing method of the adhesive sheet of this invention is demonstrated.
Although there is no restriction | limiting in particular as a manufacturing method of the adhesive sheet of this invention, Plurality which satisfies the above-mentioned requirements (Ia)-(IIa) on the viewpoint of productivity and the surface (1) of the formed resin layer From the viewpoint of facilitating the appearance or formation of the recesses (Z1) and the formation of a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) on the surface (2), at least A method having the following steps (1) and (2) is preferred.
Step (1): On the release material (R1), a coating film (x ′) composed of a composition (x) containing a resin as a main component, and a coating composition (y) comprising 15% by mass or more of the fine particles. Step of forming film (y ′) Step (2): Step of simultaneously drying coating film (x ′) and coating film (y ′) formed in step (1)

<Step (1)>
Step (1) comprises a coating film (x ′) comprising a composition (x) containing a resin as a main component on the release material (R1), and a composition (y) comprising 15% by mass or more of the fine particles. This is a step of forming a coating film (y ′).
The composition (x) is a material for forming the resin part (X), and preferably contains a crosslinking agent together with the above-mentioned resin, and may further contain the above-mentioned general-purpose additives.
The composition (y) is a material for forming the particle portion (Y), but may further contain a resin, a crosslinking agent, and the above-mentioned general-purpose additives. The composition (y) containing components such as these resins also serves as a material for forming the resin portion (X).

(Composition (x))
Examples of the resin contained in the composition (x) include resins constituting the above-described resin portion (X). Adhesive resins and resins having functional groups are preferable, and acrylic resins having the above-described functional groups ( One or more types selected from A) and rubber-based resins are more preferable, and one or more types selected from the above-mentioned acrylic copolymers (A1) and polyisobutylene-based resins are more preferable.
The content of the resin in the composition (x) is usually 40% by mass or more, preferably 50% by mass or more, based on the total amount of the composition (x) (100% by mass (excluding the dilution solvent)), More preferably 65% by mass or more, more preferably 75% by mass or more, further preferably 85% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass. It is as follows.

Moreover, as a crosslinking agent contained in a composition (x), although the crosslinking agent contained in the above-mentioned resin part (X) is mentioned, a composition (x) is a metal chelate type crosslinking agent and an epoxy type crosslinking | crosslinking. It is preferable that 1 or more types chosen from an agent are included, and it is more preferable that a metal chelate type crosslinking agent is included.
Furthermore, it is preferable that the composition (x) contains both the metal chelate crosslinking agent and the epoxy crosslinking agent from the viewpoint of improving the shape maintaining property of the plurality of recesses (Z1) and (Z2).
When the composition (x) contains both a metal chelate crosslinking agent and an epoxy crosslinking agent, the content ratio of the metal chelate crosslinking agent and the epoxy crosslinking agent in the composition (x) [metal chelate crosslinking agent / epoxy The cross-linking agent] is preferably 10/90 to 99.5 / 0.5, more preferably 50/50 to 99.0 / 1.0, and still more preferably 65/35 to 98.5 in terms of mass ratio. /1.5, more preferably 75/25 to 98.0 / 2.0.

  The content of the crosslinking agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin contained in the composition (x). 3 to 7.0 parts by mass.

The composition (x) may be an acrylic pressure-sensitive adhesive containing the above-mentioned functional group-containing acrylic resin (A) and a crosslinking agent (B), or a rubber-based pressure-sensitive adhesive containing the above-mentioned rubber-based resin. Preferably, it is an acrylic pressure-sensitive adhesive containing the above-mentioned acrylic copolymer (A1) and a crosslinking agent (B), or a rubber-based pressure-sensitive adhesive containing the above-mentioned polyisobutylene resin.
The details of the acrylic pressure-sensitive adhesive and the rubber-based pressure-sensitive adhesive are as described above.

The composition (x) may contain the above-mentioned fine particles, but the content of the fine particles is less than 15% by mass and more than the content of the resin contained in the composition (x). Few.
The specific fine particle content is less than 15% by mass, preferably 0 to 13% by mass, based on the total amount of the composition (x) (100% by mass (excluding the dilution solvent)). More preferably, it is 0-10 mass%, More preferably, it is 0-5 mass%, More preferably, it is 0 mass%.

(Composition (y))
The composition (y) is a material for forming the particle portion (Y), and contains at least 15% by mass of the above-mentioned fine particles. From the viewpoint of fine particle dispersibility, the composition (y) preferably contains a resin together with the fine particles. It is more preferable to contain a crosslinking agent together with the resin. Moreover, the composition (y) may contain a general purpose additive.
In addition, these resin, a crosslinking agent, and a general purpose additive become a forming material of resin part (X).

Examples of the fine particles contained in the composition (y) include those described above. From the viewpoint of forming a void portion (Z) in the resin layer and improving the blister resistance, silica particles are used. One or more selected from metal oxide particles and smectite are preferred.
The content of the fine particles in the composition (y) is such that the composition (y) is formed on the surface (α) of the resin layer from the viewpoint of facilitating the formation of an irregular recess formed by self-formation of the resin layer. However, it is preferably 20 to 100% by mass, more preferably 25 to 90% by mass, and still more preferably 30 to 85%. The mass is more preferably 35 to 80% by mass.

As resin contained in a composition (y), the same thing as resin contained in the above-mentioned composition (x) is mentioned, It is preferable that the same resin as composition (x) is included. In addition, you may use these resin individually or in combination of 2 or more types.
Further, as a more specific resin contained in the composition (y), a resin having a functional group is preferable, an acrylic resin (A) having the above-described functional group is more preferable, and the above-mentioned acrylic copolymer (A1) is more preferable.

  The content of the resin in the composition (y) is usually 1 to 85% by mass, preferably 5 to 80% by mass with respect to the total amount of the composition (y) (100% by mass (excluding the dilution solvent)). %, More preferably, it is 10-75 mass%, More preferably, it is 20-70 mass%, More preferably, it is 25-65 mass%.

Moreover, as a crosslinking agent contained in a composition (y), although the crosslinking agent contained in the above-mentioned resin part (X) is mentioned, a composition (y) is a metal chelate type crosslinking agent and an epoxy-type crosslinking. It is preferable that 1 or more types chosen from an agent are included, and it is more preferable that a metal chelate type crosslinking agent is included.
Furthermore, the composition (y) preferably contains both a metal chelate crosslinking agent and an epoxy crosslinking agent.
In addition, when composition (y) contains both a metal chelate type crosslinking agent and an epoxy type crosslinking agent, suitable content ratio (mass ratio) of the metal chelate type crosslinking agent and epoxy type crosslinking agent in composition (y) Is the same as that of the above-mentioned composition (x).
The content of the cross-linking agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.00 with respect to 100 parts by mass of the resin contained in the composition (y). 3 to 7.0 parts by mass.

(Formation method of coating film (x ′), (y ′))
In addition, when forming a coating film, in order to make it easy to form a coating film, it is preferable to mix | blend a solvent with composition (x) and (y), and make it the form of the solution of a composition.
Examples of such a solvent include water and organic solvents.
Examples of the organic solvent include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, t-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane. . These solvents may be used alone or in combination of two or more.

The order of laminating the coating films (x ′) and (y ′) formed on the release material (R1) in this step is not particularly limited, but the coating film (y ′) and the coating film are applied on the release material (R1). The film (x ′) is preferably formed so as to be laminated in this order.
As a method for forming the coating films (x ′) and (y ′), after the coating film (y ′) is formed, the coating film (x ′) may be sequentially formed on the coating film (y ′). Further, from the viewpoint of productivity, a method of simultaneously forming the coating film (y ′) and the coating film (x ′) with a multilayer coater may be used.
Examples of the coater used for sequential formation include spin coater, spray coater, bar coater, knife coater, roll coater, knife roll coater, blade coater, gravure coater, curtain coater, and die coater.
Examples of the coater used for simultaneous application with a multilayer coater include a curtain coater and a die coater. Among these, a die coater is preferable from the viewpoint of operability.

In this step (1), after forming at least one of the coating film (x ′) and the coating film (y ′) on the release material (R1), before moving to the step (2), the coating film You may perform the predrying process of the grade which does not advance hardening reaction.
In this step (1), the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not proceed, but preferably in step (2). Is lower than the drying temperature. The specific drying temperature indicated by the definition of “below the drying temperature in step (2)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.

<Step (2)>
Step (2) is a step of simultaneously drying the coating film (x ′) and the coating film (y ′) formed on the release material (R1) in the step (1).
In this step, by simultaneously drying the formed coating film (x ′) and coating film (y ′), a resin layer containing the resin part (X) and the particle part (Y) is formed, and A plurality of recesses (Z2) are formed on the surface (2) of the resin layer. In addition, since the plurality of recesses (Z2) are formed, the plurality of recesses (Z1) are likely to appear on the surface (1) of the resin layer when the release material (R1) is removed.

As a drying temperature in this step, a viewpoint of easily forming a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIb) on the surface (2) of the resin layer to be formed, and a release material ( From the viewpoint of facilitating the appearance of a plurality of recesses (Z1) on the surface (1) of the resin layer when R1) is removed, it is preferably 35 to 200 ° C, more preferably 60 to 180 ° C, still more preferably. It is 70-160 degreeC, More preferably, it is 80-140 degreeC.
When the drying temperature is 35 ° C. or higher, a plurality of recesses (Z2) are easily formed on the surface (2). As a result, when the release material (R1) is removed, the surface (1) of the resin layer is removed. In addition, a plurality of recesses (Z1) are likely to appear. On the other hand, if the said drying temperature is 200 degrees C or less, the malfunction that the base material and peeling material which an adhesive sheet has shrink | contracts can be suppressed.
Note that the lower the drying temperature, the larger the maximum height difference of the recesses (Z2) formed on the surface (2), but the number of the recesses (Z2) formed tends to decrease.

A void portion (Z) can be formed around the particle portion (Y) of the resin layer formed by this step.
The void portion (Z) can be easily formed by using at least one selected from silica particles, metal oxide particles, and smectite as the fine particles contained in the composition (y).

By laminating the base material or release material (R2) on the surface (2) of the resin layer formed by this step, the first of the present invention as shown in FIG. 1 (a) or (b) is obtained. An adhesive sheet is obtained.
When the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention is removed, a plurality of the above-described recesses (Z1) appear on the surface (1) of the resin layer.
Therefore, by removing the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention and causing a plurality of recesses (Z1) to appear, by laminating the release material on the surface (1) of the resin layer again, The 2nd adhesive sheet of this invention as shown in Drawing 2 (a) or (b) can be manufactured.
In addition, after removing the release material (R1), as the release material to be laminated on the surface (1) of the resin layer, the removed release material may be used again, or a separate release material may be used.

Moreover, like the 1st adhesive sheet 1a etc. of Fig.1 (a), the layer (X1) mainly containing the resin part (X), the layer (Y1) containing 15 mass% or more of particle parts (Y), and When manufacturing a pressure-sensitive adhesive sheet having a resin layer formed by forming a multilayer structure in which layers (X2) mainly including a resin portion (X) are laminated in this order, the following first and second modes are used. A manufacturing method is preferred.
In the description of the production methods of the first and second aspects below, “the composition (x1) or (x2) containing a resin as a main component” is the same as the above-described composition (x), and the composition The details of each component contained in the product (x1) or (x2) (type of component, suitable component, component content, etc.) are also the same. The “composition (y) containing 15% by mass or more of fine particles” is also as described above.

[Production Method of First Embodiment]
The manufacturing method of the first aspect includes at least the following steps (1A) and (2A).
Step (1A): A coating film (x1 ′) comprising a composition (x1) containing a resin as a main component on the release material (R1), and a coating film comprising a composition (y) containing 15% by mass or more of the fine particles. (Y ′) and a coating film (x2 ′) made of a composition (x2) containing a resin as a main component in this order, a process step (2A): a coating film formed in the step (1A) ( x1 ′), coating film (y ′), and coating film (x2 ′) are simultaneously dried.

Also in the step (1A), it is preferable that the composition (x1), the composition (y), and the composition (x2) are mixed with the above-described solvent to form a solution of the composition and then applied. .
However, from the viewpoint of adjusting the elastic modulus of the resin portion (X) on the surface (1) of the resin layer to be formed in the above range, the composition (x) that is a forming material on the surface (1) side of the resin layer is It is preferable to use a rubber-based adhesive containing a rubber-based resin.

  As a formation method of a coating film (x1 '), a coating film (y'), and a coating film (x2 '), after forming a coating film (x1') on a peeling material (R1), a coating film (x1 A method of sequentially forming using the above coater, such as forming a coating film (y ') on the coating film (y) and forming a coating film (x2') on the coating film (y '), may be used. The film (x1 ′), the coating film (y ′), and the coating film (x2 ′) may be formed by simultaneous application using the multilayer coater described above.

In this step (1A), after forming one or more coating films (x1 ′), coating film (y ′), and coating film (x2 ′), before moving to step (2A), You may perform the predrying process of the grade which the hardening reaction of the said coating film does not advance.
For example, after each of the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) is formed, the above pre-drying treatment may be performed each time. ) And the coating film (y ′), and after the above pre-drying treatment, the coating film (x2 ′) may be formed.
In this step (1A), the drying temperature at the time of performing the pre-drying treatment is usually appropriately set in a temperature range in which the formed coating film does not cure, but preferably in step (2A). Is lower than the drying temperature. The specific drying temperature indicated by the prescription “less than the drying temperature in step (2A)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and still more preferably 15 to 30 ° C.

  The step (2A) is a step of simultaneously drying the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) formed in the step (1A). The range is the same as in step (2) above. By this step, a resin layer including the resin portion (X) and the particle portion (Y) is formed.

By laminating a base material or a release material (R2) on the surface (2) of the resin layer formed by this step (2A), as shown in FIG. 1 (a) or (b), A 1st adhesive sheet is obtained.
Moreover, after removing the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention and causing a plurality of recesses (Z1) to appear, by laminating the release material on the surface (1) of the resin layer again, The 2nd adhesive sheet of this invention as shown in Drawing 2 (a) or (b) can be manufactured.

[Production Method of Second Aspect]
As a manufacturing method of a 2nd aspect, it has the following process (1B) and (2B) at least.
Step (1B): A coating film comprising a composition (y) containing 15% by mass or more of the fine particles on a layer (X1) mainly containing the resin portion (X) provided on the release material (R1). Step (2B): A coating film (y2) formed by laminating and forming a coating film (x2 ′) composed of a composition (x2) containing a resin as a main component in this order (y ′) ') And coating film (x2') are simultaneously dried

In the step (1B), the “layer (X1) mainly including the resin portion (X)” is formed by drying the coating film (x1 ′) made of the composition (x1) including the resin as the main component. be able to.
Since the layer (X1) is formed from the composition (x1), the layer (X1) may contain a crosslinking agent, a general-purpose additive and the like in addition to the resin. The content of the resin portion (X) in the layer (X1) is as described above.
However, from the viewpoint of adjusting the elastic modulus of the resin portion (X) on the surface (1) of the resin layer to be formed in the above range, the composition (x) that is a forming material on the surface (1) side of the resin layer is It is preferable to use a rubber-based adhesive containing a rubber-based resin.

As a method for forming the layer (X1), a coating film (x1 ′) made of a composition (x1) containing a resin as a main component is formed on the release material (R1), and the coating film (x1 ′) is dried. Can be formed.
There is no restriction | limiting in particular as drying temperature at this time, Preferably it is 35-200 degreeC, More preferably, it is 60-180 degreeC, More preferably, it is 70-160 degreeC, More preferably, it is 80-140 degreeC.

In this embodiment, the coating film (y ′) and the coating film (x2 ′) are formed in this order on the layer (X1) obtained after drying, not on the coating film (x1 ′). This is different from the first aspect described above.
Also in the step (1B), it is preferable that the composition (y) and the composition (x2) are mixed with the above-mentioned solvent to form a solution of the composition and then applied.
As a method for forming the coating film (y ′) and the coating film (x2 ′), after forming the coating film (y ′) on the layer (X1), the coating film (x2 ′) is formed on the coating film (y ′). ) May be sequentially formed using the above-described coater, or the coating (y ′) and the coating (x2 ′) may be simultaneously applied and formed using the above-described multilayer coater. Good.

In addition, in this process (1B), after formation of a coating film (y ') or after formation of a coating film (y') and a coating film (x2 '), before moving to a process (2B), of the said coating film You may perform the predrying process of the grade which does not advance hardening reaction.
In this step (1B), the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not cure, but preferably in step (2B). Is lower than the drying temperature. The specific drying temperature indicated by the definition of “below the drying temperature in step (2B)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.

  The step (2B) is a step of simultaneously drying the coating film (y ′) and the coating film (x2 ′) formed in the step (1B). The preferred range of the drying temperature in this step is the above-described step (2). ). By this step, a resin layer including the resin portion (X) and the particle portion (Y) is formed.

By laminating a base material or a release material (R2) on the surface (2) of the resin layer formed by this step (2B), as shown in FIG. 1 (a) or (b), A 1st adhesive sheet is obtained.
Moreover, after removing the release material (R1) of the first pressure-sensitive adhesive sheet of the present invention and causing a plurality of recesses (Z1) to appear, by laminating the release material on the surface (1) of the resin layer again, The 2nd adhesive sheet of this invention as shown in Drawing 2 (a) or (b) can be manufactured.

[Adhesive sheet of another embodiment of the present invention]
As another aspect of the 1st adhesive sheet of this invention, the adhesive sheets (1A)-(5A) shown to the following [1A]-[5A] are mentioned, for example. The details of the constituent elements of the pressure-sensitive adhesive sheets (1A) to (5A) are as described above.

[1A] On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (1A) having a plurality of concave portions (Z2) having a maximum height difference.

[2A] A resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on a release material (R1), and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (2A) having a plurality of concave portions (Z2) having a maximum height difference.

[3A] On the release material (R1), a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a base material or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having an irregular appearance,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (3A) having a plurality of concave portions (Z2) having a maximum height difference.

[4A] On the release material (R1), a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a base material or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a shape, the shape of the pasting surface on the surface (1) exposed of the resin layer is indefinite,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (4A) having a plurality of concave portions (Z2) having a maximum height difference.

[5A] On the release material (R1), a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a base material or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a length of one or more of the recesses (Z1) appearing in the region (P1) extend to any side of a square having a side of 5 mm, which is a boundary line of the region (P1). And
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (5A) having a plurality of concave portions (Z2) having a maximum height difference.

  As another aspect of the 2nd adhesive sheet of this invention, the adhesive sheets (1B)-(5B) shown to the following [1B]-[5B] are mentioned, for example. About the detail of each component of these adhesive sheets (1B)-(5B), it is as above-mentioned.

[1B] A resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on a release material (R1), and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1),
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (1B) having a plurality of concave portions (Z2) having a maximum height difference.

[2B] A resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on the release material (R1), and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1),
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (2B) having a plurality of concave portions (Z2) having a maximum height difference.

[3B] A resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles on a release material (R1), and a substrate or a release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) (Z1) is irregularly present,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (3B) having a plurality of concave portions (Z2) having a maximum height difference.

[4B] On the release material (R1), a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1), and the shape of the sticking surface on the exposed surface (1) of the resin layer is indefinite,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (4B) having a plurality of concave portions (Z2) having a maximum height difference.

[5B] On the release material (R1), a resin layer (X) containing a resin as a main component and a particle portion (Y) made of fine particles, and a substrate or release material ( R2) and at least the surface (1) of the resin layer on the side provided with the release material (R1) is an adhesive sheet having adhesiveness,
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1), and one or more of the recesses (Z1) existing in the region (P1) extend to any side of a square with a side of 5 mm, which is a boundary line of the region (P1).
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet (5B) having a plurality of concave portions (Z2) having a maximum height difference.

  The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples. In addition, the physical-property value in the following manufacture examples and Examples is a value measured by the following method.

<Mass average molecular weight of resin (Mw)>
Using a gel permeation chromatograph device (product name “HLC-8020” manufactured by Tosoh Corporation), the value measured under the following conditions and measured in terms of standard polystyrene was used.
(Measurement condition)
Column: “TSK guard column HXL-L”, “TSK gel G2500HXL”, “TSK gel G2000HXL”, “TSK gel G1000HXL” (both manufactured by Tosoh Corporation), column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min

<Measurement of volume average secondary particle diameter of silica particles>
The volume average secondary particle diameter of the silica particles was determined by measuring the particle size distribution by a Coulter counter method using a multisizer three machine (manufactured by Beckman Coulter, Inc.).

<Measurement of resin layer thickness>
The thickness of the resin layer was measured by observing the cross section of the resin layer of the target pressure-sensitive adhesive sheet using a scanning electron microscope (manufactured by Hitachi, Ltd., product name “S-4700”).

Production example x-1
(Preparation of resin composition solution (x-1))
Contains acrylic resin (i) (acrylic copolymer having structural units derived from butyl acrylate (BA) and acrylic acid (AA), BA / AA = 90/10 (mass%), Mw: 470,000) To 100 parts by mass (solid content: 33.6 parts by mass) of a mixed solution of toluene and ethyl acetate having a solids concentration of 33.6% by mass, an aluminum chelate-based crosslinking agent (product name “M-5A”, Research Institute) 5 parts by mass (solid content: 0.74 parts by mass with respect to 100 parts by mass of the acrylic resin (i)) was added to isopropyl alcohol (IPA). Was added to prepare a resin composition solution (x-1) having a solid content concentration of 28% by mass.

Production Example x-2
(Preparation of resin composition solution (x-2))
Polyisobutylene resin (PIB-i) (product name “Opanol B50”, manufactured by BASF Corporation, Mw: 340,000) 100 parts by mass (solid content) with respect to polyisobutylene resin (PIB-ii) (product name 10 parts by mass (solid content ratio) of “Opanol B30”, manufactured by BASF Corporation, Mw: 200,000, and hydrogenated petroleum resin (product name “Arcon P-100”, manufactured by Arakawa Chemical Industries, Ltd., softening point: (100 ° C.) was added in an amount of 20 parts by mass (solid content ratio), and toluene was added to prepare a resin composition solution (x-2) having a solid content concentration of 20% by mass.

Production Example x-3
(Preparation of resin composition solution (x-3))
Acrylic resin (ii) (butyl copolymer (BA), 2-ethylhexyl acrylate (2EHA), vinyl acetate (VAc), and an acrylic copolymer having structural units derived from acrylic acid (AA), BA / 2EHA / 100 parts by mass of a mixed solution of toluene and ethyl acetate having a solid content concentration of 43.0% by mass containing VAc / AA = 46/37/10/7 (mass%), Mw: 370,000) (solid content: 43.3%). 0 parts by mass), 4.5 parts by mass of the aluminum chelate crosslinking agent (product name “M-5A”, manufactured by Soken Chemical Co., Ltd., solid content concentration: 4.95% by mass) (the acrylic resin ( ii) 0.12 parts by mass of 1002 parts by mass of solid content) and an epoxy-based crosslinking agent (product name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd., solid content concentration: 5% by mass). 3 quality Addition of parts by weight (0.035 parts by mass of solid content to 100 parts by mass of the acrylic resin (ii)), isopropyl alcohol (IPA) is added, and a resin composition solution having a solid content concentration of 34.4% by mass is added. (X-3) was prepared.

Production Example y-0
(Preparation of fine particle dispersion (y-0))
Solution containing acrylic resin (i) (acrylic copolymer having structural units derived from butyl acrylate (BA) and acrylic acid (AA) (BA / AA = 90/10 (mass%), Mw: 470,000) ) Containing 100 parts by mass (solid content: 33.6 parts by mass) of 100 parts by mass (a mixed solution of toluene and ethyl acetate having a solids concentration of 33.6% by mass) containing silica particles (product name “Nip Seal E”). -200A ”, manufactured by Tosoh Silica Co., Ltd., volume average secondary particle size: 3 μm), 50.4 parts by mass (solid content: 50.4 parts by mass) and toluene were added to disperse the fine particles, and acrylic A fine particle dispersion (y-0) containing a solid resin and silica particles and having a solid content concentration of 30% by mass was prepared.

Production Examples y-1 and 2
(Preparation of coating solutions (y-1) to (y-2) for forming a coating film (y ′))
The fine particle dispersion (y-0) prepared in Production Example y-0 in the blending amount (solid content) shown in Table 1, the above-mentioned acrylic resin (i) solution, and an aluminum chelate-based crosslinking agent (product name “M” −5A ”, manufactured by Soken Chemical Co., Ltd., solid content concentration: 4.95% by mass), and a dilution solvent of the type shown in Table 1 is added, and the solid content concentration and fine particle concentration shown in Table 1 are applied. Coating liquids (y-1) to (y-2) for forming a film (y ′) were prepared.
The details of the dilution solvent used in Table 1 are as follows.
IPA: isopropyl alcohol (IPA).
IPA / CHN: Mixed solvent consisting of isopropyl alcohol (IPA) and cyclohexanone (CHN) (IPA / CHN = 60/40 (mass ratio)).

Examples 1-5
(1) Formation of coating film As a release material (R1), a release film (manufactured by Lintec Corporation, product name “SP-PET381031”, thickness 38 μm, a silicone release agent layer is provided on one side of a polyethylene terephthalate (PET) film. Was used.
On the release agent layer of the release film, using an applicator, the resin composition solution (x-1) or (x-2) prepared in Production Example x-1 or x-2 of the type shown in Table 2 is used. Then, the coating film (x1 ′) was formed by coating so that the thickness of the coating film after coating (thickness of the coating film in a non-dried state) was the thickness shown in Table 2.
Next, on the formed coating film (x1 ′), using an applicator, the coating solution (y-1) for forming the coating film (y ′) prepared in Production Example y-1 is overcoated. The film (x1 ′) and the coating film (y ′) were applied so that the total thickness of the two layers (the total thickness of the two layers in the non-dried state) was the thickness shown in Table 2, and the coating film (y ') Formed.
And on the formed coating film (y ′), using an applicator, the resin composition solution (x-1) prepared in Production Example x-1 is overcoated with the coating film (x1 ′) The coating film (y ′) and the coating film (x2 ′) were applied so that the total thickness of the three layers (the total thickness of the three layers in the non-dried state) was the thickness shown in Table 2. x2 ′) was formed.
(2) Drying treatment Thereafter, the three-layer coating film (x1 ′), coating film (y ′), and coating film (x2 ′) were simultaneously dried at a drying temperature of 100 ° C. for 2 minutes to obtain a resin part (X ) And a particle portion (Y), and a pressure-sensitive adhesive sheet having a resin layer having a thickness shown in Table 2 was produced.
(3) Back surface treatment PET film (product name “FNS Poppy, manufactured by Lintec Co., Ltd.) having an aluminum vapor deposition layer on one side as a base material on the exposed surface (2) of the resin layer formed after the drying treatment. N50 ”and a thickness of 50 μm) were laminated so as to be bonded to the aluminum vapor-deposited layer, thereby producing an adhesive sheet.

Example 6
(1) Formation of layer (X1) As release material (R1), a release film (product of Lintec Co., Ltd., product name “SP-PET381031”, thickness 38 μm, provided with a silicone release agent layer on one side of a PET film ) Was used.
On the release agent layer of the release film, using an applicator, the thickness of the coating film after coating the resin composition solution (x-1) prepared in Production Example x-1 (of the non-dried coating film) The film was applied so that the thickness was 25 μm, and a coating film (x1 ′) was formed. And it was made to dry for 2 minutes at the drying temperature of 100 degreeC, and the layer (X1) containing the resin part (X) was formed. Furthermore, it laminates so that the surface of the formed layer (X1) and the release agent layer of another peeling film of the same kind as the above may be bonded, and the laminated body which has a layer (X1) was once produced.
(2) Formation of coating film Next, the coating film prepared in Production Example y-1 was used on the surface of the layer (X1) exposed by peeling off the release film laminated on the above laminate, using an applicator. (Y ′) The coating liquid (y-1) for forming the total thickness of the two layers of the coating film (x1 ′) and the coating film (y ′) before drying (the total thickness of the two layers in the non-dried state) ) Was applied to a thickness shown in Table 2 to form a coating film (y ′).
And using the applicator on the formed coating film (y ′), the solution (x-1) of the resin composition prepared in Production Example x-1 is converted into the coating film (x1 ′) and the coating film before drying. (Y ′) and the coating film (x2 ′) were applied so that the total thickness (total thickness of the three layers in the non-dried state) of the three layers was the thickness shown in Table 2, and the coating film (x2 ′ ) Was formed.
(3) Drying treatment Thereafter, the two-layer coating films (y ′) and (x2 ′) are simultaneously dried at a drying temperature of 100 ° C. for 2 minutes to obtain a resin part (X) and a particle part (Y). In addition, a resin layer having a thickness shown in Table 2 was formed.
(4) Back surface treatment And the aluminum of the PET film which provided the aluminum vapor deposition layer on the single side | surface of the same kind as what was used in Example 1 as a base material on the surface (2) which the said resin layer has exposed Lamination was performed so as to be bonded to the vapor deposition layer, and a pressure-sensitive adhesive sheet with a substrate was produced.

Comparative Example 1
In Example 1, the coating film (y ′) and the coating film (x2 ′) were not formed, and a knife coater was used on the release agent layer of the above-described release film used as the release material (R1). The solution (x-1) of the resin composition prepared in -1 was applied so that the film thickness after drying was 25 μm, and a coating film (x1 ′) was formed in the same manner as in Example 1. Then, a pressure-sensitive adhesive sheet with a base material having a resin layer having a thickness of 25 μm and consisting only of the resin portion (X) was produced.

Comparative Example 2
(1) Formation of Resin Layer As a release material (R1), a release film (product name “SP-PET 381031” manufactured by LINTEC Corporation, thickness 38 μm, a silicone release agent layer is provided on one side of a polyethylene terephthalate (PET) film) Was used.
On the release agent layer of the release film, using an applicator, the resin composition solution (x-1) prepared in Production Example x-1 was applied to form a coating film (x1 ′), and then 100 ° C. And dried for 2 minutes to form a layer (X1) having a thickness of 5 μm including the resin portion (X).
Separately from the above, on the release agent layer of the same type of release film as described above, the coating solution (y ′) forming coating solution (y-1) prepared in Production Example y-1 was applied using an applicator. After forming the coating film (y ′), it was dried at 100 ° C. for 2 minutes to form a layer (Y1) having a thickness of 15 μm including the resin part (X) and the particle part (Y).
Furthermore, separately from the above, the resin composition solution (x-1) prepared in Production Example x-1 was applied onto the release agent layer of the same type of release film as described above using an applicator, and a coating film ( After forming x2 ′), the film was dried at 100 ° C. for 2 minutes to form a layer (X2) having a thickness of 5 μm including the resin portion (X).
And it laminated so that the surface of the layer (X1) formed on the peeling material (R1) and the surface which the layer (Y1) formed as mentioned above exposed may be bonded. Furthermore, the release film on the layer (Y1) was removed, and the surface of the exposed layer (Y1) was laminated to the exposed surface of the layer (X2) formed as described above.
In this manner, the layer (X1), the layer (Y1), and the layer (X2) are laminated in this order on the release material (R1), and the resin part (X) and the particle part (Y) are included. A resin layer having a thickness of 25 μm was formed.
(2) Back surface treatment And the aluminum of the PET film which provided the aluminum vapor deposition layer on the single side | surface of the same kind as what was used in Example 1 as a base material on the layer (X2) which the said resin layer has exposed. Lamination was performed so as to be bonded to the vapor deposition layer, and a pressure-sensitive adhesive sheet with a substrate was produced.

Examples 7-8
(1) Formation of coating film As the release material (R1), a release film (product name “SP-PET381031”, thickness 38 μm, manufactured by Lintec Co., Ltd., with a silicone release agent layer provided on one side of the PET film) is used. Using.
On the release agent layer of the release film, the resin composition solution (x-3) prepared in Production Example x-3 and the coating solution (y ′) forming coating solution (y) prepared in Production Example y-2 -2) and the resin composition solution (x-3) prepared in Production Example x-3 at the same flow rate and coating speed shown in Table 3 in this order using a multilayer die coater (width: 250 mm) simultaneously. It applied and laminated | stacked simultaneously in order of the coating film (x1 '), the coating film (y'), and the coating film (x2 ') from the peeling material (R1) side.
(2) Drying treatment Then, the three-layer coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously dried at a drying temperature of 100 ° C. for 2 minutes to obtain a resin portion (X ) And a particle portion (Y), and a resin layer having a thickness shown in Table 3 was formed.
(3) Back surface treatment And the aluminum of the PET film which provided the aluminum vapor deposition layer on the single side | surface of the same kind as what was used in Example 1 as a base material on the surface (2) which the said resin layer has exposed Lamination was performed so as to be bonded to the vapor deposition layer, and a pressure-sensitive adhesive sheet with a substrate was produced.

Example 9
(1) Formation of layer (X1) As release material (R1), a release film (product of Lintec Co., Ltd., product name “SP-PET381031”, thickness 38 μm, provided with a silicone release agent layer on one side of a PET film ) Was used.
On the release agent layer of the release film, the resin composition solution (x-1) prepared in Production Example x-1 was applied using an applicator to form a coating film (x1 ′). And it was made to dry for 2 minutes at the drying temperature of 100 degreeC, and the 8-micrometer-thick layer (X1) containing the resin part (X) was formed. Furthermore, it laminates so that the surface of the formed layer (X1) and the release agent layer of another peeling film of the same kind as the above may be bonded, and the laminated body which has a layer (X1) was once produced.
(2) Formation of coating film Next, the coating film (y ′) formed in Production Example y-1 was formed on the surface of the layer (X1) that was exposed by peeling off the release film laminated earlier of the laminate. The coating solution (y-1) for coating and the solution (x-1) of the resin composition prepared in Production Example x-1 were in this order multi-layer die coater (width: 500 mm) at the flow rates and coating speeds shown in Table 3. ) And simultaneously laminated in the order of the coating film (y ′) and the coating film (x2 ′) from the layer (X2) side.
(3) Drying treatment Thereafter, the two-layer coating films (y ′) and (x2 ′) are simultaneously dried at a drying temperature of 100 ° C. for 2 minutes to obtain a resin part (X) and a particle part (Y). In addition, a resin layer having a thickness shown in Table 3 was formed.
(4) Back surface treatment And the aluminum of the PET film which provided the aluminum vapor deposition layer on the single side | surface of the same kind as what was used in Example 1 as a base material on the surface (2) which the said resin layer has exposed Lamination was performed so as to be bonded to the vapor deposition layer, and a pressure-sensitive adhesive sheet with a substrate was produced.

  The following measurements or observations were performed on the resin layers of each pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples. These results are shown in Tables 2 and 3.

<Mass retention rate of resin layer of adhesive sheet>
In each Example and Comparative Example, the release material (R1) was removed before the base material was laminated (before the back surface treatment) to obtain a single resin layer.
And after measuring the mass of the resin layer before a heating, the said resin layer was thrown into the muffle furnace (The Denken company make, product name "KDF-P90"), and it heated at 800 degreeC for 30 minutes. And the mass of the resin layer after a heating was measured and the mass retention of the resin layer was computed by the following formula.
Mass retention of resin layer (%) = [mass of resin layer after heating] / [mass of resin layer before heating] × 100

<Elastic modulus at 23 ° C. of the resin portion (X) on the surface (1)>
Regarding the elastic modulus at 23 ° C. of the resin part (X) on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples, “J. Vac. Soc. Jpn. Vol. 56, No. 7, 2013 p258 Ken Nakajima Measured in accordance with the elastic modulus measurement method described in “Development of quantitative evaluation method for elastic modulus of soft materials by atomic force microscope”. In addition, the said measurement is performed 5 times (arbitrary 5 points | pieces), and the average value of the value of 5 times is described in Table 2 and Table 3. At that time, when a value that can be clearly determined as the elastic modulus of the fine particles was obtained instead of the resin portion (X), the measurement was repeated except for the value.

More specifically, a scanning probe microscope (manufactured by Shimadzu Corporation, product name “SPM-9700”) and a cantilever (manufactured by TEAM NANOTEC, product name “LRCH 250”, spring constant: 0.3 N / m, thermal fluctuation) (Measured value by the method: 0.24 N / m, probe tip radius 300 nm), and measured at a frequency of 4 Hz.
In the force curve measurement, the relationship between the amount of warpage of the cantilever and the amount of displacement of the piezo scanner when the cantilever is pushed into the resin portion (X) and when it is pulled away can be obtained.
The obtained force curve is converted into a relationship between the load (F) and the sample deformation amount (δ) as an F-δ curve. The F-δ curve is a Johnson-Kendall-Roberts (JKR) two-point method. Was analyzed.
In the JKR two-point method, the elastic modulus E of the sample can be obtained by the following equation from two points of an equilibrium point (point A) and an adhesion point (point B) in the separation process. If the coordinates of A and B are defined as A (δ ₀ , 0) and B (δ ₁ , F ₁ ), respectively, the elastic modulus E can be calculated from the following equation.

(In the above formula, ν is the Poisson's ratio of the sample, and is 0.5 in this embodiment. R is the radius of curvature of the tip of the cantilever probe, and is 300 nm in this embodiment.)

<Shape of recess (Z1) on surface (1)>
When the release material (R1) of the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples is removed, the following requirements (Ia) to (IIa) in the specific regions defined by the requirements on the surface (1) of the resin layer Observation is made using a scanning electron microscope (manufactured by Hitachi, Ltd., product name “S-4700”, requirement (IIa) at 30 × magnification). did.
In Tables 2 and 3, when it is determined that a recess (Z1) satisfying each requirement is formed, “A”, it is determined that the presence of the recess (Z1) satisfying each requirement is not recognized. The case is described as “F”.
Requirement (Ia): There are a plurality of concave portions (Z1) having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square of 5 mm on an arbitrarily selected side on the surface (1).
Requirement (IIa): Total number of a plurality of concave portions (Z1) having a maximum height difference of 100 nm or more and existing in a region (P1) surrounded by a square of 5 mm on an arbitrarily selected side on the surface (1) ( 100%), when the number of recesses (Z1) having different shapes is 95% or more (100%), that is, all the recesses (Z1) in the region (P1) have different shapes. Is written as “A +” in the table).
Of the maximum height difference values of the plurality of recesses (Z1) measured during the evaluation of the requirement (Ia), the largest value is described as “maximum height difference value” in Tables 2 and 3. .

<Shape of recess (Z2) on surface (2)>
In the examples and comparative examples, the concave portions satisfying the following requirements (Ib) to (IIIb) in specific regions defined by the requirements on the surface (2) of the resin layer before laminating the base material (before the back surface treatment) Whether (Z2) was formed was observed using a scanning electron microscope (manufactured by Hitachi, Ltd., product name “S-4700”, requirement (IIb) was observed at a magnification of 30 times).
In Tables 2 and 3, when it is determined that a recess (Z2) satisfying each requirement is formed, “A”, it is determined that the presence of the recess (Z2) satisfying each requirement is not recognized. The case is described as “F”.
Requirement (Ib): There are a plurality of concave portions (Z2) having a maximum height difference of 0.5 μm or more in a region (P2) surrounded by a square of 5 mm on an arbitrarily selected side on the surface (2).
Requirement (IIb): of a plurality of concave portions (Z2) having a maximum height difference of 0.5 μm or more existing in a region (P2) surrounded by a square of 5 mm on an arbitrarily selected side on the surface (2) When the number of recesses (Z2) having different shapes is 95% or more (100%) with respect to the total number (100%), that is, all the recesses (Z2) in the region (P2) have different shapes. If it has, it is described as “A +” in the table).
Requirement (IIIb): One or more recesses (Z2) having a maximum height difference of 0.5 μm or more exist in a region (Q2) surrounded by a square of 1 mm on an arbitrarily selected side on the surface (2) To do.
Of the maximum height difference values of the plurality of recesses (Z2) measured during the evaluation of requirement (Ib), the largest value is described as “maximum height difference value” in Tables 2 and 3. .

<Area ratio of affixed portion on the surface (1)>
As the “translucent adherend having a smooth surface”, alkali-free glass (product name “Eagle XG”, manufactured by Corning Inc.) was used.
Five values calculated through the following operations (i) to (iii) are obtained, and the average value of these five values is regarded as the “area ratio of the pasted portion on the surface (1)” of the target adhesive sheet. It was. The measurement results of each Example and Comparative Example are shown in Table 2 and Table 3.
Operation (i): As shown in FIG. 5A, on the smooth surface 101a of the translucent adherend 101, the surface (1) 121 of the resin layer 12 included in the pressure-sensitive adhesive sheets produced in Examples and Comparative Examples. Left to touch. And it reciprocates 5 times with the 2kg roller (crimping device prescribed | regulated by JISZ0237: 2000 10.2.4) with respect to the base-material 13 side of the said adhesive sheet, and the surface (1) 121 of the resin layer 12 and The translucent adherend 101 was stuck to the smooth surface 101a. And the laminated body 100 installed in the direction as shown to Fig.5 (a) was obtained.
Operation (ii): In a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) 121 from the translucent adherend 101 side of the laminate 100 obtained in operation (i). Using a digital microscope (manufactured by Keyence Corporation, product name “Digital Microscope VHX-1000”), from the W direction in FIG. 5A, the smooth surface 101a of the translucent adherend 101 and the surface of the resin layer (1) The interface with 121 was photographed to obtain a digital image of the selected area (P1). The photographing was performed by dividing the selected area (P1) into square blocks each having a side of 0.5 mm and photographing a total of 100 blocks. In addition, a total of five areas were selected as the area (P1), and five types of digital images were acquired.
Operation (iii): Each digital image obtained is subjected to image processing (binarization processing) using image analysis software (product name “Image-Pro Plus” manufactured by Media Cybernetics), and binarized image Got. Then, based on the binarized image, the area S of the affixed portion in contact with the smooth surface of the translucent adherend in the entire area of the selected region (P1) is obtained, and the calculation formula “[Attach Based on “area ratio of part (%)] = S / total area of selected region (P1) × 100”, the ratio of the area of the selected region (P1) attached to the translucent adherend is calculated. did.
Tables 2 and 3 show the average values of the “area ratio of the pasted portion on the surface (1)” obtained by performing the same operation for each of the five types of digital images.

<Shape of the pasted portion on the surface (1)>
With respect to the pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples, the translucent adherend 101 side of the laminate 100 prepared in the “operation (i)” in the measurement of the “area ratio of the pasted portion on the surface (1)” above. Thus, the state of the surface (1) of the resin layer of each pressure-sensitive adhesive sheet was observed visually in the W direction of FIG. The shape of the pasted portion on the surface (1) was evaluated according to the following criteria.
A: It can be visually determined that the shape of the affixed part with the smooth surface of the translucent adherend on the surface (1) can be visually recognized and that the affixed part has an indefinite shape.
B: Although the shape of the sticking part with the smooth surface of the translucent adherend on the surface (1) can be visually confirmed, the shape of the sticking part is not indefinite.
C: The shape of the pasting part with the smooth surface of the translucent adherend on the surface (1) cannot be visually confirmed.

  About each adhesive sheet produced by the Example and the comparative example, "air bleeding property", "blister resistance", and "adhesive force" were measured or evaluated based on the following methods. These results are shown in Tables 2 and 3.

<Air escape characteristics>
A pressure-sensitive adhesive sheet with a base material having a size of 50 mm long × 50 mm wide was affixed to a melamine coating plate as an adherend so that air retention occurred. And the presence or absence of the air pocket after crimping | compression-bonding using a squeegee was observed, and the air release property of each adhesive sheet was evaluated with the following references | standards.
A: The air pocket has disappeared, and the air release property is excellent.
F: An air pocket remains and the air release property is inferior.

<Blister resistance>
Adhesive sheet with base material measuring 50 mm long × 50 mm wide is affixed to a polymethyl methacrylate plate (product name “Acrylite L001”, manufactured by Mitsubishi Rayon Co., Ltd.) 70 mm long × 150 mm wide × 2 mm thick. A test sample was prepared by pressure bonding using
This test sample was allowed to stand at 23 ° C. for 12 hours, then left in an 80 ° C. hot air dryer for 1.5 hours, and further left in a 90 ° C. hot air dryer for 1.5 hours, after heating was promoted. The blister generation state was visually observed, and the blister resistance of each pressure-sensitive adhesive sheet was evaluated according to the following criteria.
A: No blisters were confirmed.
B: A blister was partially confirmed.
C: Blister was confirmed on the entire surface.

<Adhesive strength>
After the adhesive sheet with a base material produced in Examples and Comparative Examples was cut into a size of 25 mm in length and 300 mm in width, the surface (2) of the resin layer of the adhesive sheet was 23 ° C. and 50% RH (relative humidity). Was attached to a stainless steel plate (SUS304, No. 360 polishing) and allowed to stand for 24 hours in the same environment. After standing, the adhesive force of each adhesive sheet was measured at a pulling speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000.

According to Tables 2 and 3, the pressure-sensitive adhesive sheets produced in Examples 1 to 9 have a plurality of recesses (Z1) satisfying the requirements (Ia) to (IIa) on the surface (1), and the surface (2 ), It was confirmed that a plurality of recesses (Z2) satisfying the above requirements (Ib) to (IIIb) were present, and all of air bleedability, blister resistance, and adhesive strength were good.
Moreover, in any of the adhesive sheets produced in Examples 1 to 9, the release material (R1) is removed, and the inside of the region (P1) on the surface (1) of the exposed resin layer is the above scanning electron microscope ( When observed with a magnification of 30 times, it was confirmed that a plurality of recesses (Z1) appeared irregularly and existed, and the shape of the pasting surface in the region (P1) on the surface (1) was It was irregular.

  In addition, in any of the pressure-sensitive adhesive sheets produced in Examples 1 to 9, the release material (R1) was removed, and the recesses (Z1) that appeared in the region (P1) on the surface (1) of the exposed resin layer ) Extend to one side of a 5 mm square that is the boundary line of the region (P1), and is surrounded by a 5 mm square adjacent to the region (P1). It was confirmed to have a shape extending continuously into the region (P1 ′).

  Moreover, in Example 1-9, when the surface (2) on the resin layer before laminating a base material (before a back surface process) was observed visually, it was confirmed that multiple recessed part (Z2) exists. Furthermore, in visually observing the surface (2) of the resin layer, the plurality of recesses (Z2) exist irregularly, and the shape of the surface excluding the plurality of recesses (Z2) is irregular. It was also confirmed.

7 and 8 are images when observed with a scanning electron microscope after removing the release material (R1) of the pressure-sensitive adhesive sheet produced in Example 1. FIG. FIG. 7A is a cross-sectional image near the surface (1) side of the resin layer of the pressure-sensitive adhesive sheet, and FIG. 7B is a perspective image of the surface (1) of the resin layer of the pressure-sensitive adhesive sheet. Moreover, Fig.8 (a) is a perspective image of the surface (1) seen from the side surface side of the resin layer of the said adhesive sheet, FIG.8 (b) is an enlarged image of Fig.8 (a).
As shown in the images shown in FIGS. 7 and 8, on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet produced in Example 1, after removing the release material (R1), a plurality of recesses appeared and existed. I understand that

On the other hand, FIG. 9A is a cross-sectional image in the vicinity of the surface (2) side of the resin layer of the pressure-sensitive adhesive sheet produced in Example 1, and FIG. 9B is the surface (2) of the resin layer of the pressure-sensitive adhesive sheet. ) Is a perspective image. In the image of FIG. 9A, the length of 20.0 μm is shown for the 10 scales shown in the lower right of the image, and in the image of FIG. 9B, the length is shown in the lower right of the image. The length of 500 μm is indicated by 10 divisions.
As can be seen from the image shown in FIG. 9, a plurality of concave portions are formed on the surface (2) of the resin layer of the pressure-sensitive adhesive sheet produced in Example 1. The image in FIG. 9 is obtained by photographing before laminating the base material on the surface (2) of the resin layer (before the back surface treatment) in order to confirm the presence of the recess on the surface (2) of the resin layer. It is a thing.

10 is an image of the pressure-sensitive adhesive sheet produced in Example 8 when observed with a scanning electron microscope after removing the release agent (R1), and FIG. 10 (a) is a resin layer of the pressure-sensitive adhesive sheet. FIG. 10B is a perspective image of the surface (2) of the resin layer of the pressure-sensitive adhesive sheet. In addition, in the image of Fig.10 (a), (b), the length of 1.00 mm is shown for the 10 scales described in the lower right in the said image.
As shown in the image shown in FIG. 10, on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet produced in Example 8, after removing the release material (R1), a plurality of recesses appeared and existed. It can be seen that a plurality of recesses are also formed on the surface (2).
In addition, also in the image of FIG. 10B, in order to confirm the presence of the concave portion on the surface (2) of the resin layer, before laminating the base material on the surface (2) of the resin layer (before the back surface treatment). It was obtained by shooting.

On the other hand, the formation of specific recesses was not recognized on the surface of the resin layer included in the pressure-sensitive adhesive sheets prepared in Comparative Examples 1 and 2, and the air release performance was inferior. Further, the pressure-sensitive adhesive sheet of Comparative Example 1 was inferior in blister resistance.
FIG. 11 is an image when the pressure-sensitive adhesive sheet produced in Comparative Example 1 is observed with a scanning electron microscope, where (a) is a cross-sectional image of the pressure-sensitive adhesive sheet, and (b) is the surface of the resin layer of the pressure-sensitive adhesive sheet. It is a perspective image of (1). In the image of FIG. 11 (a), the length of 20.0 μm is shown on the 10 scales shown in the lower right in the image, and in the image of FIG. 11 (b), shown in the lower right of the image. The length of 500 μm is indicated by 10 divisions.
As shown in the image shown in FIG. 11, no concave portion was found on the surface (1) of the resin layer of the pressure-sensitive adhesive sheet produced in Comparative Example 1.

  The pressure-sensitive adhesive sheet of one embodiment of the present invention is useful as a pressure-sensitive adhesive sheet having a large pasting area, which is used for identification or decoration, for coating masking, for protecting a surface of a metal plate or the like.

1a, 1b, 2a, 2b Adhesive sheet 11 Release material (R1)
12 resin layer 121 surface (1)
122 Surface (2)
(X) Resin part (X)
(Y) Particle part (Y)
(X1) Layer (X1) mainly containing resin part (X)
(X2) Layer (X2) mainly containing resin part (X)
(Y1) Layer (Y1) containing 15% by mass or more of the particle part (Y)
13 Substrate 14 Release material (R2)
21, 210, 211, 212 Recess (Z1)
21a Intersection 22, 221, 222 Recess (Z2)
50, 501, 502, 503, 504, 505 One side of 5 mm square 51 Non-sticking part 52 Sticking part

Claims (34)

On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a shape, and 95% or more of the plurality of recesses (Z1) appearing in the region (P1) have shapes different from each other,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet in which a plurality of concave portions (Z2) having a maximum height difference exist, and 95% or more of the plurality of concave portions (Z2) present in the region (P2) have different shapes. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1), and 95% or more of the plurality of recesses (Z1) present in the region (P1) have shapes different from each other,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet in which a plurality of concave portions (Z2) having a maximum height difference exist, and 95% or more of the plurality of concave portions (Z2) present in the region (P2) have different shapes.   The pressure-sensitive adhesive sheet according to claim 1, wherein the shape of the sticking surface on the exposed surface (1) of the resin layer is indefinite.   When the release material (R1) is removed and the exposed surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted, the permeation on the surface (1) is adhered. The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein an area ratio of a part to be adhered to the smooth surface of the photosensitive adherend is 60 to 99.999%.   When the release material (R1) is removed and the exposed surface (1) of the resin layer and the smooth surface of the translucent adherend having a smooth surface are pasted, the permeation on the surface (1) is adhered. The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the shape of the part to be adhered to the smooth surface of the optical adherend is indefinite.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the plurality of recesses (Z1) appear or exist irregularly on the surface (1) of the resin layer.   One or more of the recesses (Z1) appearing or existing in the region (P1) on the surface (1) extend to any side of a square with a side of 5 mm, which is a boundary line of the region (P1). Item 7. The pressure-sensitive adhesive sheet according to any one of items 1 to 6.   One or more other regions (P1) in which one or more of the recesses (Z1) appearing or existing in the region (P1) on the surface (1) are surrounded by a square with a side of 5 mm adjacent to the region (P1). ') The pressure-sensitive adhesive sheet according to claim 7, wherein the pressure-sensitive adhesive sheet has a continuously extending shape.   The region according to any one of claims 1 to 8, wherein at least one recess (Z2) is present in a region (Q2) surrounded by a square with a side of 1 mm arbitrarily selected on the surface (2). Adhesive sheet.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the resin contained in the resin portion (X) includes a pressure-sensitive adhesive resin.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 10, wherein the resin contained in the resin portion (X) includes a resin having a functional group.   The pressure-sensitive adhesive sheet according to claim 11, wherein the functional group is a carboxyl group.   The pressure-sensitive adhesive sheet according to claim 11 or 12, wherein the resin portion (X) further contains one or more selected from a metal chelate crosslinking agent and an epoxy crosslinking agent.   The pressure-sensitive adhesive sheet according to any one of claims 11 to 13, wherein the resin portion (X) contains both a metal chelate crosslinking agent and an epoxy crosslinking agent.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 14, wherein the fine particles are one or more selected from silica particles, metal oxide particles, and smectites.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 15, wherein a surface (2) of the resin layer has adhesiveness, and a release material (R2) is laminated on the surface (2).   The pressure-sensitive adhesive sheet according to any one of claims 1 to 16, wherein a mass retention after heating the resin layer at 800 ° C for 30 minutes is 3 to 90 mass%.   The pressure-sensitive adhesive sheet according to any one of claims 1 to 17, wherein the surface of the release material (R1) that is in contact with the surface (1) of the resin layer is a release-treated surface on which an uneven shape is not formed. .   The pressure-sensitive adhesive sheet according to any one of claims 1 to 18, wherein the concave portion (Z2) is not formed by transferring an embossed pattern.   The resin layer comprises, from the release material (R1) side, a layer (X1) mainly containing a resin part (X), a layer (Y1) containing 15% by mass or more of a particle part (Y), and a resin part (X The pressure-sensitive adhesive sheet according to any one of claims 1 to 19, which has a multilayer structure in which layers (X2) containing) are laminated in this order. The layer (X1) is a layer formed from a composition containing a resin as a main component,
The layer (Y1) is a layer formed from a composition containing 15% by mass or more of fine particles,
The pressure-sensitive adhesive sheet according to claim 20, wherein the layer (X2) is a layer formed from a composition containing a resin as a main component. It is a method of manufacturing the adhesive sheet as described in any one of Claims 1-19, Comprising: The manufacturing method of an adhesive sheet which has at least following process (1) and (2).
Step (1): On the release material (R1), a coating film (x ′) composed of a composition (x) containing a resin as a main component, and a coating composition (y) comprising 15% by mass or more of the fine particles. Step (2) for forming film (y ′): Step of simultaneously drying coating film (x ′) and coating film (y ′) formed in step (1) It is a method of manufacturing the adhesive sheet of Claim 21, Comprising: The manufacturing method of an adhesive sheet which has the following process (1A) and process (2A) at least.
Step (1A): A coating film (x1 ′) composed of a composition (x1) containing a resin as a main component on a release material (R1), and a coating film (y) composed of a composition (y) containing 15% by mass or more of fine particles ( Step (2A): A coating film (x1) formed by laminating and forming a coating film (x2 ′) composed of a composition (x2) containing resin as a main component in this order y ′) '), The step of simultaneously drying the coating film (y') and the coating film (x2 ') It is a method of manufacturing the adhesive sheet of Claim 21, Comprising: The manufacturing method of an adhesive sheet which has the following process (1B) and process (2B) at least.
Step (1B): A coating film comprising a composition (y) containing 15% by mass or more of the fine particles on a layer (X1) mainly containing the resin portion (X) provided on the release material (R1). Step (2B): A coating film (y2) formed by laminating and forming a coating film (x2 ′) composed of a composition (x2) containing a resin as a main component in this order (y ′) ') And coating film (x2') are simultaneously dried On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having an irregular appearance,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a shape, the shape of the pasting surface on the surface (1) exposed of the resin layer is indefinite,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
When the release material (R1) is removed, a maximum height difference of 100 nm or more in a region (P1) surrounded by a 5 mm square arbitrarily selected on the surface (1) of the exposed resin layer A plurality of recesses (Z1) having a length of one or more of the recesses (Z1) appearing in the region (P1) extend to any side of a square having a side of 5 mm, which is a boundary line of the region (P1). And
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1),
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1),
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) (Z1) is irregularly present,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1), and the shape of the sticking surface on the exposed surface (1) of the resin layer is indefinite,
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference. On the release material (R1), a resin layer containing a resin part (X) containing a resin as a main component and a particle part (Y) made of fine particles, and a substrate or release material (R2) on the resin layer And having a pressure-sensitive adhesive sheet on the surface (1) of the resin layer on the side provided with at least the release material (R1),
The elastic modulus at 23 ° C. of the resin part (X) on the surface (1) is 1.0 × 10 ^{3 to} 8.0 × 10 ⁸ Pa,
A concave portion having a maximum height difference of 100 nm or more in a region (P1) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (1) of the resin layer on the side provided with the release material (R1) There are a plurality of (Z1), and one or more of the recesses (Z1) existing in the region (P1) extend to any side of a square with a side of 5 mm, which is a boundary line of the region (P1).
In a region (P2) surrounded by a square with a side of 5 mm arbitrarily selected on the surface (2) of the resin layer on the side where the substrate or release material (R2) is provided, 0.5 μm or more A pressure-sensitive adhesive sheet having a plurality of concave portions (Z2) having a maximum height difference.