TWI719057B - Adhesive sheet and manufacturing method of adhesive sheet - Google Patents

Abstract

The present invention provides an adhesive sheet, which has a resin layer on a substrate or release material, and has adhesiveness at least on the surface (α) of the resin layer opposite to the side on which the substrate or release material is provided Adhesive sheet, and the surface (α) has a concave portion and a flat surface with a flat portion outside the concave portion. The flat portion is slightly parallel to the surface laminated with the resin layer of the substrate or release material, on the surface (α) In the arbitrarily selected area (D) surrounded by a rectangle with a length of 8 mm × a width of 10 mm, there are plural flat surfaces. Among the aforementioned plural flat surfaces, the smaller area of each flat surface is removed from the area (D). If the total of the surrounding lengths of more than one flat surface is set to 100, the standard deviation relative to the average value of the surrounding lengths of all the flat surfaces is a flat surface with a cumulative relative frequency of 30% or less. 0.33 or more.

Description

Adhesive sheet and manufacturing method of adhesive sheet

The invention relates to an adhesive sheet and a manufacturing method of the adhesive sheet.

A general adhesive sheet is composed of a substrate, an adhesive layer formed on the substrate, and a release material provided on the adhesive layer as required. When in use, when the release material is provided, the The peeling material abuts and sticks the adhesive layer to the adherend.

However, when attaching an adhesive sheet with a large application area, such as for identification and decoration, for coating and masking, for surface protection of metal plates, etc., to the adherend, between the adhesive layer and the adherend Air accumulates easily and becomes "bulging" in this part, and there is a problem that the adhesive sheet is not easy to adhere to the adherend beautifully.

In order to solve these problems, for example, Patent Document 1 discloses that the surface of the adhesive layer is in contact with a release material with a fine embossing pattern, and the surface of the adhesive layer is formed by artificially arranging grooves of a specific shape with a specific pattern. The adhesive flakes.

By using these adhesive sheets, it occurs when attaching to the body to be adhered "Air accumulation" can be released to the outside through the grooves artificially formed on the surface of the adhesive layer.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Special Publication No. 2001-507732

However, as described in Patent Document 1, an adhesive sheet having an adhesive layer with grooves of a general specific shape arranged in a specific pattern, if the groove width is narrow, the air is not easily removed, and if the groove width is large, it is not only due to the surface The base material is recessed to deteriorate the appearance, and there is also a problem of reduced adhesion.

Moreover, since the adhesive sheet is arranged with grooves in a specific pattern, the adhesive force of the part where the grooves are arranged locally deteriorates. When the adhesive sheet is attached to the adherend, there is a possibility of peeling from the part.

On the other hand, when the adhesive sheet is attached to the adherend and then peeled off, since the adhesive properties of the adhesive sheet are locally different, it depends on the peeling direction of the adhesive sheet, which may cause residual paste on the adherend. Yu. For example, in the case of an adhesive sheet having an adhesive layer in which grooves are arranged in a grid, if it is peeled off in an oblique direction, there is a possibility of residual paste on the adherend.

Furthermore, when the adhesive sheet is press-processed, there is a possibility that the groove layout pattern and the press-processed pattern overlap. In this case, there is a problem that the depth of the cut marks varies, and cut marks cannot be appropriately formed on the adhesive sheet.

And, generally, in order to make the release material provided in the adhesive sheet contain It is easy to peel, and sometimes a step (so-called spine cutting) is performed where only cut marks are applied to the peeling material and the starting point for peeling is set. When performing this step, generally the release material is temporarily peeled off from the adhesive sheet, and after cutting the release material, the release material and the adhesive layer of the adhesive sheet are laminated again.

However, the adhesive sheet described in Patent Document 1 uses an embossed liner as a release material. Therefore, when the release material and the adhesive layer are laminated again, it is difficult to follow the embossed pattern of the release material, so it is necessary to prepare for it. Another release material with embossing processing.

Furthermore, in Patent Document 1, in order to form a fine structure on the adhesive layer, an adhesive is applied to the embossed pad once to form an adhesive layer, and then the adhesive layer is laminated with the base material (the so-called Transfer coating method). However, when a substrate having a low-polar surface such as a polyolefin-based substrate is used as the above-mentioned substrate, sufficient adhesion cannot be obtained at the interface between the substrate and the adhesive layer by this method.

In addition, unlike the release material made of paper, it is difficult to form a fine embossing pattern on the adhesive layer with the release material made of a resin film.

The object of the present invention is to provide an adhesive sheet with excellent degassing properties and good adhesive properties that can easily remove the air trapped when it is attached to an adherend, and a manufacturing method of the adhesive sheet.

The inventors of the present invention found that the following adhesive sheet can solve the above-mentioned problems, and thus completed the present invention. The adhesive sheet has an adhesive property An adhesive sheet with a resin layer with recesses and a plurality of flat surfaces on the surface, and a flat surface that is less than 30% of the cumulative relative frequency obtained by removing the smaller area of each flat surface and adding the relative frequency. The standard deviation of the average value of the surrounding length of the above flat surface or the standard deviation of the average value relative to the area of the flat surface is adjusted to a specific value or more.

That is, the present invention provides the following [1] to [28].

[1] An adhesive sheet having a resin layer on a substrate or release material, and having adhesiveness at least on the surface (α) of the resin layer opposite to the side on which the substrate or release material is provided Adhesive sheet, and there are recesses and a plurality of flat surfaces on the surface (α). On the surface (α), the arbitrarily selected area (D) surrounded by a rectangle of length 8mm×width 10mm, there is a plurality of flat surfaces Surface, and the aforementioned plural flat surfaces satisfy at least one of the following requirements (1) and (2): ‧Requirement (1): remove the aforementioned plural flat surfaces from the smaller area of each flat surface and add the relative A flat surface with a cumulative relative frequency of 30% or less based on the number of times. If the sum of the surrounding lengths of more than one flat surface (S) is set to 100, the average value relative to the surrounding length of the flat surface (S) The standard deviation of the above is 0.33 or more; ‧Requirement (2): Remove the flat surface of less than 30% of the cumulative relative frequency obtained by adding the relative frequency from the smaller area of each flat surface from the aforementioned plural flat surfaces. When the total area of one or more flat surfaces (S) is set to 100, the standard deviation relative to the average area of the flat surfaces (S) is 0.39 or more.

[2] The adhesive sheet as in [1] above, which meets the aforementioned requirements at the same time (1) and (2).

[3] The adhesive sheet described in [1] or [2] above, which satisfies the aforementioned requirement (1), and also satisfies the following requirements (1-1): ‧Requirement (1-1): each flat surface (S The skewness Sk value of) relative to the normal distribution curve of surrounding length and frequency is 1.0 or more.

[4] The adhesive sheet mentioned in [3] above, which satisfies the aforementioned requirement (1), and at the same time satisfies the following requirements (1-2): ‧Requirement (1-2): Relative to each flat surface (S) The kurtosis Ku value of the normal distribution curve of surrounding length and frequency is 0.3 or more.

[5] The adhesive sheet described in [1] or [2] above, which satisfies the aforementioned requirement (2), and also satisfies the following requirements (2-1): ‧Requirement (2-1): Each flat surface (S The skewness Sk value of the normal distribution curve with respect to area and frequency is 1.0 or more.

[6] The adhesive sheet as in [5] above, which satisfies the aforementioned requirement (2), and at the same time satisfies the following requirements (2-2): ‧Requirement (2-2): Each flat surface (S) is relative to The kurtosis Ku value of the normal distribution curve of area and frequency is above 1.8.

[7] The adhesive sheet according to any one of [1] to [6] above, wherein the shape of the flat surface viewed from the surface (α) side is amorphous.

[8] The adhesive sheet as described in any one of [1] to [7] above, in which an area (P) on the surface (α) surrounded by a square of 5 mm on one side (P) is arbitrarily selected, and the area (P) that passes through the square At least one of the two cross-sections (P1) obtained by cutting the aforementioned adhesive sheet in the thickness direction on a diagonal line and on a plane perpendicular to the area (P) on the surface (α), On the surface (α) side of the aforementioned section (P1), there is a maximum height difference of more than 40% of the total thickness of the aforementioned resin layer, and the shape of the cut part is different from each other. The cut portion of the aforementioned flat surface existing in ), and the surface that is in contact with the aforementioned resin layer of the aforementioned substrate or release material is a substantially parallel flat portion.

[9] The adhesive sheet according to [8] above, wherein in the cross section (P1), there are a plurality of flat portions on the surface (α) side.

[10] The adhesive sheet according to [9] above, wherein in the cross section (P1), the positions of the plurality of flat portions existing on the surface (α) side do not have periodicity.

[11] The adhesive sheet of [9] or [10] above, wherein in the cross-section (P1), the distance from the respective plurality of flat portions on the surface (α) side to the substrate or release material For the same.

[12] The adhesive sheet according to any one of [8] to [11] above, wherein when a plurality of the aforementioned cross sections (P1) are obtained, there exists on the surface (α) side of the respective cross sections (P1) The formation position and formation length of the flat part are different from each other in the obtained plural section (P1).

[13] The adhesive sheet according to any one of [1] to [12] above, wherein the concave portion has a maximum height difference of 0.5 μm or more.

[14] The adhesive sheet according to any one of [1] to [13] above, wherein there are more than one flat surface (f1) on the surface (α) of the resin layer, and the flat surface (f1) has the option of The width of the area enclosed by a circle with a diameter of at least 100μm.

[15] The adhesive sheet according to any one of [1] to [14] above, wherein there are more than one flat surface (f2) on the surface (α) of the resin layer, and the flat surface (f2) has 0.2 mm ² The above area.

[16] The adhesive sheet according to any one of [1] to [15] above, wherein the aforementioned recesses are not formed by using a release material with an embossed pattern.

[17] The adhesive sheet according to any one of [1] to [16] above, wherein the resin layer includes a resin portion (X) containing resin and a particle portion (Y) composed of fine particles.

[18] The adhesive sheet of the above [17], wherein in the cross section (P1), the particle portion (Y) contained in the resin layer has a non-uniform distribution in the horizontal direction and is relatively present on the surface The concave part of (α), the distribution of the particle part (Y) in the area (s1) below the concave part in the thickness direction is at the same level as the area (s1) and the area with a flat part on the surface (α) (s2) Compared to less.

[19] The adhesive sheet of [17] or [18] above, wherein the mass retention rate of the resin layer after heating at 800° C. for 30 minutes is 3 to 90% by mass.

[20] The adhesive sheet according to any one of [17] to [19] above, wherein the resin contained in the resin part (X) contains an adhesive resin.

[21] The adhesive sheet according to any one of [17] to [20] above, wherein the resin portion (X) further contains one or more selected from the group consisting of a metal chelate crosslinking agent and an epoxy crosslinking agent .

[22] The adhesive sheet of any one of [17] to [21] above, wherein the aforementioned fine particles are selected from silica particles, metal oxide particles, and bentonite One or more of them.

[23] The adhesive sheet according to any one of [1] to [22] above, wherein the surface (β) of the resin layer on the side where the substrate or release material is provided has adhesiveness.

[24] The adhesive sheet according to any one of [1] to [23] above, wherein the resin layer is from the side where the base material or the release material is provided, in accordance with the layer (Xβ), which mainly contains the resin portion (X), A layer (Y1) containing 15% by mass or more of the particle portion (Y) and a layer (Xα) mainly containing the resin portion (X) are laminated in this order.

[25] The adhesive sheet of the above-mentioned [24], wherein the layer (Xβ) is a layer formed of a composition (xβ) containing resin and the content of fine particles is less than 15% by mass, and the layer (Y1) is composed of 15 The layer formed by the composition (y) with a mass% or more, and the layer (Xα) is a layer formed with the composition (xα) containing a resin and the content of fine particles is less than 15% by mass.

[26] A method for manufacturing an adhesive sheet, which is a method for manufacturing an adhesive sheet as described in any one of [1] to [24] above, and has at least the following steps (1) and (2); step (1) : Form a coating film (x') composed of a composition (x) containing resin and having a content of fine particles less than 15% by mass, and a coating film (x') composed of a composition (y) containing 15 mass% or more of fine particles ( Step y'); Step (2): Simultaneously dry the coating film (x') and the coating film (y') formed in step (1).

[27] A method of manufacturing an adhesive sheet, which is a method of manufacturing the adhesive sheet as described in [25] above, and has at least the following steps (1A) and (2A): Step (1A): on a substrate or release material According to the coating film (xβ') composed of the composition (xβ) containing resin and the content of fine particles less than 15% by mass, and the coating film (y) composed of the aforementioned composition (y) containing 15 mass% or more of fine particles '), and a step of laminating a coating film (xα') composed of a composition (xα) containing a resin and a content of fine particles less than 15% by mass; step (2A): simultaneously using the steps (1A) The step of drying the formed coating film (xβ'), coating film (y'), and coating film (xα').

[28] A method of manufacturing an adhesive sheet, which is the method of manufacturing an adhesive sheet as described in [25] above, and has at least the following steps (1B) and (2B): Step (1B): Set on a substrate or peel off On the layer (Xβ) that mainly contains the resin part (X) on the material, the coating film (y') composed of the aforementioned composition (y) containing 15% by mass or more of fine particles, and the content of fine particles containing resin The step of laminating the coating film (xα') composed of the composition (xα) of less than 15% by mass; step (2B): simultaneously using the coating film (y') formed in step (1B) And the coating film (xα') is dried.

When the adhesive sheet of the present invention is attached to an adherend, it can easily remove possible air accumulation, has excellent degassing properties and has good adhesive properties.

1a, 11a, 12a, 1b, 2a, 2b‧‧‧Adhesive sheet

11‧‧‧Substrate

12‧‧‧Resin layer

12a‧‧‧surface (α)

12b‧‧‧Surface (β)

(X)‧‧‧Resin part (X)

(Y)‧‧‧Particle part (Y)

(Xβ)‧‧‧Layer (Xβ) mainly containing resin part (X)

(Xα)‧‧‧Layer (Xα) mainly containing resin part (X)

(Y1)‧‧‧Layer (Y1) containing 15% by mass or more of particles (Y)

13, 13a, 131, 132‧‧‧Concavity

14‧‧‧Flat surface

14a‧‧‧flat part

15‧‧‧Protrusion

21、22‧‧‧Peeling material

50‧‧‧square

51, 52‧‧‧ diagonal

Section 60‧‧‧(P1)

Section 61, 62‧‧‧

100‧‧‧Transparent adhered body

100a‧‧‧Smooth surface

101‧‧‧Adhesive body

FIG. 1 is a schematic cross-sectional view of the adhesive sheet showing an example of the structure of the adhesive sheet of the present invention.

2 is a schematic plan view of the surface (α) when viewed from the surface (α) side of the resin layer of the adhesive sheet of the present invention.

3 is a schematic cross-sectional view of the resin layer showing an example of the shape of the resin layer surface (α) side of the adhesive sheet of the present invention.

FIG. 4 is a diagram for explaining the method of obtaining "two cross-sections of the adhesive sheet" specified in this specification, and is a perspective view of the adhesive sheet in the same state of the present invention.

Fig. 5 is an example of a schematic diagram of the section (P1) specified in this specification.

Fig. 6 is a cross-sectional view of the measurement sample used in the observation of the resin layer surface (α) of the adhesive sheet made in the embodiment and the comparative example.

Figure 7(a) is a digital microscope taken from the surface (α) side of the exposed surface (α) of the resin layer of the adhesive sheet produced in Example 1 and the area surrounded by a rectangle of 8mm long x 10mm wide (D) ) Binary image of the resulting image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part. Figure 7(b) is a cross-sectional image obtained by observing the cross-section of the adhesive sheet made in Example 1 using a scanning microscope.

Figure 8 uses a digital microscope to photograph the exposed surface (α) of the resin layer of the adhesive sheet produced in Example 2 from the surface (α) side of the area (D) surrounded by a arbitrarily selected rectangle with a length of 8 mm × a width of 10 mm. Image 2 Valued image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

Figure 9 uses a digital microscope to photograph the exposed surface (α) of the resin layer of the adhesive sheet produced in Example 3 from the surface (α) side of the area (D) surrounded by a arbitrarily selected rectangle with a length of 8 mm × a width of 10 mm. The binary image of the image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

Figure 10 uses a digital microscope to photograph the exposed surface (α) of the resin layer of the adhesive sheet made in Example 4 from the surface (α) side of the area (D) surrounded by a arbitrarily selected rectangle with a length of 8 mm × a width of 10 mm. The binary image of the image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

Figure 11 is a digital microscope taken from the surface (α) side of the exposed surface (α) of the resin layer of the adhesive sheet produced in Comparative Example 1 and the area (D) surrounded by a rectangle of 8mm long x 10mm wide arbitrarily selected The binary image of the image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

Figure 12 is a digital microscope taken from the surface (α) side of the exposed surface (α) of the resin layer of the adhesive sheet produced in Comparative Example 2 and the area (D) surrounded by a rectangle with a length of 8 mm × a width of 10 mm arbitrarily selected. The binary image of the image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

Figure 13 uses a digital microscope to photograph the exposed surface (α) of the resin layer of the adhesive sheet produced in Comparative Example 3 from the surface (α) side. The length of the exposed surface (α) is arbitrarily selected. The binarized image of the image obtained from the area (D) enclosed by a rectangle of 8mm×width 10mm. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

Figure 14 uses a digital microscope to photograph the exposed surface (α) of the resin layer of the adhesive sheet produced in Comparative Example 4 from the surface (α) side of the area (D) surrounded by a arbitrarily selected rectangle with a length of 8 mm × a width of 10 mm. The binary image of the image. In addition, the black part of the binary image corresponds to a flat surface, and the white part corresponds to a concave part.

In the present invention, for example, the description of "YY containing XX component as a main component" or "YY mainly composed of XX component" means "the component with the largest content among the components contained in YY is XX component". The content of the specific XX component in the record is usually 50% by mass or more relative to the total amount of YY (100% by mass), preferably 65-100% by mass, more preferably 75-100% by mass, and still more 85~100% by mass.

In the present invention, for example, "(meth)acrylic acid" means both "acrylic acid" and "methacrylic acid", and other similar terms are also the same.

Furthermore, with regard to a preferable numerical range (for example, a range of content, etc.), the lower limit and the upper limit of the stepwise description can be combined independently. For example, based on the description of "preferably 10~90, more preferably 30~60", it is also possible to combine "better lower limit value (10)" and "better upper limit value (60)" to become "10~60" .

[The composition of the adhesive sheet of the present invention]

The adhesive sheet of the present invention is an adhesive sheet having a resin layer on a substrate or release material, and at least the surface (α) of the resin layer opposite to the side where the substrate or release material is provided has adhesiveness, There are recesses and a plurality of flat surfaces on the surface (α).

FIG. 1 is a schematic cross-sectional view of the adhesive sheet showing an example of the structure of the adhesive sheet of the present invention.

As an adhesive sheet in the same state of the present invention, for example, as shown in FIG. 1(a), an adhesive sheet 1a having a resin layer 12 on a substrate 11, or as shown in FIG. 1(b), on a release material 21 The adhesive sheet 1b with the resin layer 12 thereon.

The adhesive sheet of the present invention has adhesiveness at least on the surface (α) 12a (hereinafter also referred to as "surface (α)") of the resin layer 12 on the side opposite to the side where the aforementioned substrate 11 or release material 21 is provided, and exists Recess 13 and flat surface 14.

Therefore, from the viewpoint of handling properties, as another aspect of the present invention, it is preferable to further provide a release material 22 on the surface (α) 12a of the resin layer 12 with respect to the adhesive sheets 1a and 1b shown in FIG. It becomes the structure of the adhesive sheets 2a, 2b as shown in Fig. 1(c) or (d).

Furthermore, in the adhesive sheet of the same aspect of the present invention, as shown in FIG. 1, the resin layer 12 preferably includes a resin portion (X) containing resin and a particle portion (Y) composed of fine particles.

Since the particle portion (Y) is contained in the resin layer 12, an adhesive sheet with improved burst resistance can be obtained.

The details of the resin part (X) and the particle part (Y) will be described later.

In addition, in the adhesive sheet of the present invention, the surface (β) 12b (hereinafter also referred to as "surface (β)") of the resin layer 12 on the side where the base material 11 or the release material 21 is provided may also have adhesiveness .

By making the surface (β) also adhesive, according to the adhesive sheets 1a and 2a shown in Figs. 1(a) and (c), the adhesion between the resin layer 12 and the substrate 11 is good, according to Fig. 1(b) And the adhesive sheets 1b, 2b shown in (d) can be double-sided adhesive sheets.

[Requirements for the recesses and flat surfaces on the surface (α)]

In the adhesive sheet of the present invention, as shown in FIGS. 1(a) to (d), there are recesses 13 and a plurality of flat surfaces 14 on the surface (α) 12a of the resin layer 12.

The recessed portion 13 present on the surface (α) is used as an air discharge passage for releasing the "air accumulation" generated when the surface (α) of the resin layer of the adhesive sheet of the present invention is attached to the adherend to the outside. The role of the person.

On the other hand, the flat surface 14 existing on the surface (α) is the surface that directly contacts and adheres to the adherend when it is attached to the adherend, and is the part that does not affect the adhesive force of the adhesive sheet.

2 is a schematic plan view of the surface (α) when viewed from the surface (α) side of the resin layer of the adhesive sheet of the present invention.

The concave portion present on the surface (α) of the resin layer is preferably an amorphous concave portion 13, as shown in FIG. 2, but a fixed-shaped concave portion may also be present.

However, in the same aspect of the present invention, as shown in FIG. 2, it is preferable that more than one amorphous concave portion 13 exists on the surface (α) 12a of the resin layer 12, and it is more preferable to have In a plurality of amorphous recesses 13.

The presence of amorphous recesses on the surface (α) of the resin layer can provide an adhesive sheet with improved degassing properties and adhesive properties in a more balanced manner.

In addition, by the presence of a plurality of amorphous recesses, even if a portion of the recesses on the surface (α) collapses by applying pressure from a certain direction, the recesses 13 with maintained shapes are likely to exist on the surface (α). , Can prevent the path of degassing from disappearing.

In addition, the length of the recess 13 when the recess 13 exists on the surface (α) in a plan view is not particularly limited. That is, the concave portion 13 includes a relatively long groove shape or a relatively short recessed shape.

In the same aspect of the present invention, as shown in FIG. 2, it is preferable that the shape of the flat surface 14 viewed from the surface (α) 12a side of the resin layer 12 is amorphous.

In addition, the flat surface existing on the surface (α) of the resin layer may have a fixed flat surface together with the amorphous flat surface 14, but it is preferable that a plurality of amorphous concave portions 14 exist.

Due to the presence of an amorphous flat surface on the surface of the resin layer (α), it is different from the surface of an adhesive layer formed by a peeling sheet with an embossed pattern, so that the local adhesive force is weaker or the outgassing is poor. There is as little as possible. As a result, the surface (α) of the resin layer can exhibit uniform and excellent degassing properties and adhesive properties.

In addition, in the present invention, the term "amorphous" refers to a shape without a circle or an ellipse that can be drawn at the center, and a polygonal shape. It refers to a shape whose shape is irregular and no similarity is seen in each shape. Specifically, it is the shape of the recessed portion 13 and the flat surface 14 shown in FIG. 2.

On the other hand, as those that are not "amorphous" but "fixed", examples include circles, ellipses, and polygons. In addition, in this specification, the so-called "polygon" refers to a figure that can be drawn diagonally inside (not protruding to the outside), and the sum of the inner angles is 180×n (degrees) (n is a natural number). A figure surrounded by a straight line. This polygon also includes those whose corners are curved.

In addition, in the present invention, the determination of whether there are "amorphous" recesses or flat surfaces on the surface (α) of the resin layer is in principle determined from the surface (α) side of the resin layer by visual inspection or digital microscope (magnification: 30-100 Times) Judging by observing the shape of the flat surface or concave portion of the observation object.

Also, when using a digital microscope, for example, as shown in Fig. 6, the focal point is slowly moved in the direction A from the top of the surface (α) 12a where a flat surface is visually recognized, and the part where the focal point is initially observed is suitable for observation as a flat surface. .

Moreover, when the focus cannot be determined by the above method, as shown in Figure 6(b), a squeegee can be used to paste the surface (α) 12a of the resin layer on the surface (α) 12a of the resin layer with a smooth surface as shown in Figure 6(b). The adherend 100 is judged by the method of observing the surface (α) 12a of the resin layer through the light-transmitting adherend 100 with a digital microscope, and confirming whether there are recesses and flat surfaces. That is, the part of the surface (α) that is in contact with the smooth surface 100a can be judged as a "flat surface", and the part of the surface (α) that is not in contact with the smooth surface 100a can be judged as a "concave".

However, it is also possible to select 1 to 10 areas (D) of the arbitrarily selected area (D) with a length of 8 mm × a width of 10 mm on the surface (α), from the surface (α) side Visually or digital microscope (magnification: 30~100 times) observe and judge the shape of the concave part or flat surface in each selected area (D). That is, in any selected area, if there is an amorphous recess or flat surface, it can also be regarded as "there is an amorphous recess or flat surface on the surface (α)". Similarly, in any selected area, if there are a plurality of amorphous recesses or flat surfaces, it can also be regarded as "there are a plurality of amorphous recesses or flat surfaces on the surface (α)".

In the observation of the area (D), a digital microscope can also be used to observe the entire area of the selected area (D) at a low magnification.

In addition, a digital microscope can also be used to observe the selected area (D) at high magnification. However, due to the observation at high magnification, the area (D) may be larger than the photographable area of the digital microscope. In this case, you can also use the image linking function of the digital microscope to shoot arbitrarily selected areas adjacent to each other and obtain adjacent plural images, connect the plural images into a connected image, and select any image from the connected image. The area enclosed by a rectangle with a length of 8 mm × a width of 10 mm is selected as the area (D) for the above judgment.

In addition, in the following description, in order to determine whether a certain requirement is met, when a digital microscope is used to observe the selected area, it is also possible to judge whether the requirement is met from the linked image in the same manner as described above.

In the description of this manual, as a digital microscope used for observation of various shapes, for example, the product name "Digital Microscope VHX-1000" or "Digital Microscope VHX-5000" manufactured by KYENCE Corporation.

In addition, when observing various shapes, it is also possible to directly use the digital The method of observing the surface (α) with a microscope can also be a method of using a digital microscope to obtain an image at the above-mentioned magnification, and visually observing the shape of the concave and flat portions displayed in the image.

In addition, the shape of the amorphous recesses present on the surface (α) is preferably visually recognizable from the surface (α) side.

Similarly, the amorphous flat surface shape existing on the surface (α) is preferably visually recognizable from the surface (α) side.

1(c) or (d), in the adhesive sheets 2a, 2b of the release material 22 laminated on the surface (α) 12a of the resin layer 12, when the release material 22 is removed, the exposed surface (α) ) 12a becomes a visual observer.

In the same state of the present invention, on the surface (α), as shown in FIG. 2, there may be a fixed concave part together with the amorphous concave part 13.

However, as 100% of the total area of the recesses existing on the surface (α), the area ratio of the amorphous recesses on the surface (α) is preferably 80 to 100%, more preferably 90 to 100%, and More preferably, it is 95~100%, and even better is 100%.

In addition, in the same aspect of the present invention, as 100% of the total area of the surface (α), the area ratio of the recesses existing on the surface (α) is preferably 10 to 80%, more preferably 20 to 70% , More preferably 30~60%, still more preferably 35~55%.

Similarly, in the same state of the present invention, on the surface (α), as shown in FIG. 2, a flat surface with a fixed shape may exist together with the flat surface 14 with an amorphous shape.

However, as the total area of the flat surface relative to the surface (α) 100%, the proportion of the area occupied by the amorphous flat surface on the surface (α), preferably 80-100%, more preferably 90-100%, still more preferably 95-100%, still more preferably 100% .

In addition, in the same aspect of the present invention, as 100% of the total area of the surface (α), the area ratio of the flat surface existing on the surface (α) is preferably 20 to 90%, more preferably 30 to 80 %, better still 40~70%, still better 45~65%.

In addition, the above-mentioned "proportion of area occupied by recesses or flat surfaces" can be obtained by using a digital microscope (magnification: 30-100 times) to obtain an image of the surface (α), and image processing (binarization processing) is performed on the image ) And calculated.

In addition, select 1 to 10 areas of the arbitrarily selected area (D) with a length of 8 mm × a width of 10 mm on the surface (α), and use a digital microscope (magnification: 30 to 100 times) to obtain an image of the area, from which The image calculates the value of the "proportion of area occupied by the concave portion or flat surface" of each area, and the average of the values of the selected 1-10 areas is regarded as existing on the resin layer surface (α) of the target adhesive sheet "The proportion of the area occupied by the concave portion or the flat surface."

In the same aspect of the present invention, based on the viewpoint of becoming an adhesive sheet that improves various properties such as outgassing and adhesion characteristics in a more balanced manner, it is preferable that the shape of the concave and flat portions existing on the surface (α) of the resin layer does not have Become the shape of a fixed repeating unit.

Furthermore, in the aspect of the present invention, based on the viewpoint of becoming an adhesive sheet that improves various characteristics such as outgassing and adhesion characteristics in a more balanced manner, it is preferable that there are plural concave portions on the surface (α) of the resin layer, and the plural concave portions Its location does not have periodicity. And, based on the same point of view, it is better than There are a plurality of flat surfaces on the surface (α) of the resin layer, and the existence position of the plurality of flat surfaces does not have periodicity.

In the present invention, the term "the existence position of the plural recesses or flat surfaces does not have periodicity" means that on the surface (α) of the resin layer, the existence position of the plural recesses or flat surfaces does not have the same repeating pattern, but is irregular (Random) status.

In addition, to determine whether "the shape of the concave portion and the flat portion does not have a shape that becomes a fixed repeating unit", and to determine whether the position of the plurality of concave portions or the flat surface does not have periodicity, can be determined by the above-mentioned "in the resin layer" The same method is used to determine whether there is an amorphous concave portion or a flat surface on the surface (α).

Hereinafter, the specific requirements regarding the concave portion and the flat surface existing on the surface (α) will be described.

<Regarding the specific requirements of the concave portion on the surface (α)>

In the same aspect of the present invention, there are preferably more than one amorphous recesses, more preferably a plurality of amorphous recesses, in an area surrounded by a square of 1 mm arbitrarily selected on one side of the surface (α) of the resin layer.

The presence of one or more amorphous recesses in the above-mentioned region (Q) can provide an adhesive sheet with well-balanced improvement in various properties such as degassing properties and adhesive properties.

In the same aspect of the present invention, the concave portion 13 existing on the surface (α) 12a of the resin layer 12 preferably has a maximum height difference of 0.5 μm or more.

The "concave" defined here refers to a recess with a maximum height difference of 0.5μm or more, as long as the part with the maximum height difference of 0.5μm or more is located in any part of the recess, it is not necessary to cover the entire area of the recess. It has a height difference of 0.5μm or more.

3 is a schematic cross-sectional view of the resin layer showing an example of the shape of the resin layer surface (α) side of the adhesive sheet of the present invention.

Like the recess 13 shown in FIG. 3(a), it has two mountain parts (M ₁ ), (M ₂ ), and a valley part (N) as a normal recess shape. The "maximum height difference" of the recess in the present invention means the highest position (m) of the _{two mountain parts (M 1} ) and (M _{2) in the thickness direction of the resin layer 12 (the mountain part in Figure 3(a)} The length of the difference (h) between the maximum point of (M ₁ ) and the lowest position (n) (the minimum point of the valley part (N) in Fig. 3(a)).

In addition, as in the case of Figure 3(b), it is considered that there are two mountain parts (M ₁₁ ), (M ₁₂ ) and a valley part (N ₁ ) concave part 131 and two mountain parts (M ₁₂ ), ( M _{13 ) and two} concave portions of the concave portion 132 of the valley portion (N 2 ). In this case, the length of the difference (h ₁ ) between the maximum point of the _{mountain part (M 11 ) and the minimum point of the valley part (N 1} ) represents the maximum height difference of the recess 131, and the maximum point and the valley of the _{mountain part (M 13)} The length of the minimum point difference (h ₂ ) of the portion (N ₂ ) represents the maximum height difference of the concave portion 132.

As the maximum height difference of a recess, based on the viewpoint of improving the degassing property of the adhesive sheet, the viewpoint of maintaining the appearance of the adhesive sheet, and the viewpoint of the shape stability of the adhesive sheet, it is more preferably 1.0 μm or more and the thickness of the resin layer or less, It is more preferably 3.0 μm or more and the thickness of the resin layer or less, and still more preferably 5.0 μm or more and the thickness of the resin layer or less.

In addition, as the average value of the width of the recess, based on the viewpoint of improving the degassing property of the adhesive sheet and the viewpoint that the adhesiveness of the adhesive sheet is good, it is preferably 1 to 500 μm, more preferably 3 to 400 μm, and still more preferably 5 ~300μm.

In addition, in the present invention, the width of the recess means the distance between the maximum points of the two mountain parts. In the recess 13 shown in Figure 3(a), it means the mountain part (M ₁ ) and the mountain part (M ₂ ) The distance L. In addition, in the recess 131 shown in Figure 3(b), it refers to the distance L _{1 between the mountain part (M 11} ) and the mountain part (M ₁₂ ), and the recess 132 refers to the mountain part (M ₁₃ ) and the mountain part (M ₁₂ ) is the distance L ₂ .

In addition, when the adhesive sheet of the present invention is viewed from above (when viewed from directly above), when the recess has a long side and a short side, it means the width of the short side.

As for the ratio of the maximum height difference to the average width of the concave portion [maximum height difference/average width] (in the concave portion 13 shown in Figure 3(a), it refers to "h/L"), based on the adhesive sheet The viewpoint of improving the degassing property and the viewpoint that the adhesiveness of the adhesive sheet is good, preferably 1/500~100/1, more preferably 3/400~70/3, still more preferably 1/60~10/1 .

<Regarding the unique requirements of the flat surface on which the surface (α) exists>

In the same aspect of the present invention, there are preferably more than one flat surface (f1) on the surface (α) of the resin layer, and the flat surface (f1) has a diameter that can be selected from at least 100 μm (preferably 150 μm in diameter, more preferably 150 μm in diameter). For the width of the area surrounded by a circle of 200 μm), it is better to have a plurality of the flat surfaces (f1).

Since the surface (α) has a flat surface (f1), the bonding part on the surface (α) with the adherend can be made sufficient, so it can be improved and the adherend Adhesive flakes with higher adhesion and higher adhesion.

Furthermore, in the above-mentioned embodiment of the present invention, in the area (D) surrounded by an arbitrarily selected rectangle with a length of 8 mm × a width of 10 mm on the surface (α) of the resin layer, there is preferably more than one flat surface (f1), it is better to have a plurality of the flat surfaces (f1).

In addition, in the above embodiment, it is not necessary that all the flat surfaces that exist on the surface (α) or the area (D) of the resin layer are the flat surfaces (f1), as long as they exist on the surface (α) or the area (D) The flat surface may include the flat surface (f1).

Furthermore, in another aspect of the present invention, there are ^{preferably more than one flat surface (α) having an area of 0.2 mm 2} or more (preferably 0.3 mm ² or more, more preferably 0.4 mm ² or more) on the surface (α) of the resin layer. f2), it is better to have plural flat surfaces (f2).

Due to the flat surface (f2) on the surface (α), the bonding area on the surface (α) with the adherend can be made sufficient, so the adhesion to the adherend can be improved, and the adhesive force can be higher. Adhesive flakes.

Furthermore, in the above aspect of the present invention, in the area (D) on the surface (α) of the resin layer surrounded by arbitrarily selected rectangles of 8 mm in length × 10 mm in width, there are preferably more than one flat surface ( f2), it is better to have plural flat surfaces (f2).

In addition, in the above embodiment, it is not necessary that all the flat surfaces that exist on the surface (α) or the area (D) of the resin layer are the flat surfaces (f2), as long as they exist on the surface (α) or the area (D) The flat surface should include the flat surface (f2).

In addition, in the area (D) surrounded by a randomly selected rectangle of 8mm long x 10mm wide on the surface (α) or the surface (α) of the resin layer, it is more It is preferable that one or more flat surfaces (f12) exist together with both the flat surfaces (f1) and (f2), and it is more preferable that there are plural flat surfaces (f12).

In addition, in the present invention, the determination of whether the above-mentioned flat surfaces (f1), (f2), (f12) exist on the surface (α) or the area (D) can be observed with a digital microscope (magnification: 30 to 100 times). The surface (α) or the flat surface of the area (D) of the resin layer of the adhesive sheet of the object is obtained, and an image is obtained. Based on the image, use image analysis software to determine whether the circle with a diameter of 100~200μm can be selected The enclosed area may be calculated for the area of a flat surface.

In another aspect of the present invention, on the surface (α) of the resin layer, in the area (D) surrounded by a rectangle of 8 mm long × 10 mm wide, which is arbitrarily selected, the area (D) relative to the recesses existing in the area (D) The total area is 100%, and there are recesses having an area of 70-99.99% (preferably 85-99.99%).

The presence of such continuous recesses can become an adhesive sheet with improved degassing properties.

[Each requirement satisfied by the adhesive sheet of the present invention]

In the adhesive sheet of the present invention, in the arbitrarily selected area (D) on the surface (α) of the resin layer surrounded by a rectangle with a length of 8 mm × a width of 10 mm, there are a plurality of flat surfaces, and the aforementioned plurality of flat surfaces Satisfy at least one of the following requirements (1) and (2): ‧Requirement (1): The cumulative relative number of 30 is obtained by subtracting the above plural flat surfaces from the smaller area of each flat surface and adding the relative number of times. % Less than the flat surface, and more than one flat surface (S) around the long When the total is set to 100, the standard deviation relative to the average value of the surrounding length of the flat surface (S) is 0.33 or more; ‧Requirement (2): Remove the flat surface from the above-mentioned plural flat surfaces. The smaller one is a flat surface with a cumulative relative frequency of 30% or less by adding the relative frequency. If the total area of more than one flat surface (S) is set to 100, the area relative to the flat surface (S) The standard deviation of the average is 0.39 or more.

In addition, in the same aspect of the present invention, it is preferable to satisfy the aforementioned requirements (1) and (2) at the same time.

In the present invention, the standard deviation specified by the above requirements (1) and (2) or the calculation target of the skewness and kurtosis described later is set to be among the above-mentioned plural flat surfaces, "the area of each flat surface is smaller than the The reason for obtaining more than one flat surface (S) by adding the relative frequency to a cumulative relative frequency of 30% or less" is as follows.

That is, when an image of a region (D) surrounded by a rectangle of 8 mm long x 10 mm wide is taken with a digital microscope, the flat surface at the end of the region (D) is approached by the boundary of the region (D) The 4 sides of the rectangle of the line are cut off. The "cut flat surface" changes with the selection of the area (D), and is not a flat surface that actually exists on the surface (α).

In this way, when the data of the flat surface cut by the four sides of the rectangle including the boundary line of the area (D), the data of the cut flat surface that does not exist actually increases, the data will deviate from the actual situation. Of concerns.

However, "the flat surface cut by the rectangle of the boundary of the area (D)" is almost included in "adding the relative order of the smaller area of each flat surface A flat surface with a cumulative relative frequency of less than 30%."

Therefore, in the present invention, the standard deviation, skewness, and kurtosis are not discussed for all the flat surfaces in the region (D), but the flat surface in the region (D) will be calculated from the smaller area of each flat surface. The standard deviation, skewness, and kurtosis of the "flat surface (S)" except for the "flat surface (S)" except for the "flat surface (S)" which is the cumulative relative frequency of 30% or less by adding the relative frequency Thereby, the influence of the non-existent "flat surface cut by the rectangle 50 of the boundary line of the region (D)" on the values of standard deviation, skewness, and kurtosis can be adjusted to be small.

The standard deviation relative to the average value of the surrounding length of the flat surface (S) specified by the requirement (1) represents the skewness of the distribution of the surrounding length of each flat surface (S). That is, the larger the standard deviation relative to the average value of the surrounding length of the flat surface (S), the wider the distribution of the surrounding length of more than one flat surface (S), which means that the shape of the flat surfaces (S) is very different from each other. Significant.

For example, a flat surface (S) whose surrounding length is longer than the average contributes a lot to the improvement of the adhesion of the adhesive sheet. On the other hand, a flat surface (S) with a peripheral length shorter than the average has many recesses around it. Due to the existence of the recesses, air traps that may occur when attached to the adherend are easily removed, which improves deaeration. The contribution is great.

That is, the larger the standard deviation relative to the average value of the surrounding length of the flat surface (S), it means that the flat surface (S) whose surrounding length is longer than the average value is deviated from the flat surface (S) whose surrounding length is shorter than the average value. Existing and distributed, it can have both high adhesion and degassing.

Based on the above point of view, as the standard deviation of the average value of the surrounding length of the flat surface (S) specified by the requirement (1), the standard deviation is 0.33 or more, It is preferably 0.36 or more, more preferably 0.40 or more, still more preferably 0.45 or more, and is preferably 50.00 or less, more preferably 20.00 or less, still more preferably 10.00 or less, still more preferably 5.00 or less.

In addition, the standard deviation of the area average value with respect to the flat surface (S) specified by the requirement (2) represents the skewness of the area distribution of each flat surface (S). That is, the larger the standard deviation relative to the average area of the flat surface (S), the wider the distribution of the area of more than one flat surface (S), which means that the size difference between the flat surfaces (S) is very significant.

For example, a flat surface (S) with a larger area than the average contributes a lot to the improvement of the adhesive force of the adhesive sheet. On the other hand, a flat surface (S) with an area smaller than the average has many recesses around it. Due to the existence of the recesses, air traps that may occur when attached to the adherend are easily removed, which improves the degassing performance. Great contribution.

That is, the larger the standard deviation relative to the average area of the flat surface (S), it means that the flat surface (S) with an area larger than the average value and the flat surface (S) with an area smaller than the average value are distributed in a biased manner. , Can have both high adhesion and degassing.

Based on the above viewpoint, the standard deviation of the area average value relative to the flat surface (S) specified by the requirement (2) is 0.39 or more, preferably 0.40 or more, more preferably 0.42 or more, and preferably 50.00 or less, and more It is preferably less than 20.00, more preferably less than 10.00, still more preferably less than 5.00.

In the same aspect of the present invention, the above-mentioned requirement (1) is better satisfied, and the following requirement (1-1) is further satisfied at the same time, the above-mentioned requirement (1) is better satisfied, and the following requirements (1-1) and ( 1-2).

‧Requirement (1-1): The skewness Sk value of the normal distribution curve of each flat surface (S) relative to the surrounding length and frequency is 1.0 or more (preferably 1.2 or more, more preferably 1.4 or more, and more preferably 1.6 the above).

‧Requirement (1-2): The kurtosis Ku value of the normal distribution curve of each flat surface (S) relative to the surrounding length and frequency is 0.3 or more (preferably 0.5 or more, more preferably 1.0 or more, and more preferably 1.5 the above).

Furthermore, in another aspect of the present invention, the above-mentioned requirement (2) is preferably satisfied, while the following requirement (2-1) is further satisfied, and the above-mentioned requirement (2) is better satisfied, and the following requirement (2-1) is further satisfied at the same time. ) And (2-2).

‧Requirement (2-1): The skewness Sk value of the normal distribution curve of each flat surface (S) with respect to area and frequency is 1.0 or more (preferably 1.1 or more, more preferably 1.2 or more, and more preferably 1.3 or more ).

‧Requirement (2-2): The kurtosis Ku value of the normal distribution curve of each flat surface (S) with respect to area and frequency is 1.8 or more (preferably 1.9 or more, more preferably 2.0 or more, and more preferably 2.1 or more ).

The "skewness Sk value" specified in the above requirements (I-1) and (2-1) indicates the degree of asymmetry of the statistically flat surface (S) with respect to the normal distribution curve of the surrounding length and frequency.

If the skewness Sk value = 0, the distribution curve of the surrounding length or area of the flat surface (S) and the frequency becomes a symmetrical shape.

If the skewness Sk value>0 (the skewness Sk value is a positive value), the distribution curve of the surrounding length or area of the flat surface (S) and the frequency becomes a shape that the peak is leftward, and the end of the distribution curve extends to the right.

If the skewness Sk value is less than 0 (the skewness Sk value is a negative value), then the flat surface (S) The distribution curve of surrounding length or area and frequency becomes the shape of the peak to the right, and the tail end of the distribution curve extends to the left.

In addition, the larger the absolute value of the skewness Sk value, the larger the deformation.

In the above-mentioned requirements (1-1) and (2-1), the circumference of the flat surface (S) in the area (D) is longer or the area and the frequency distribution curve is longer than the circumference of the flat surface (S) or the area The flat surface (S) with the smaller average value of the surrounding length or area deforms, which means that the surrounding length or area of the flat surface (S) has a wider range of distribution.

Such a wide distribution of the surrounding length or area of each flat surface (S) is considered to be due to the existence of a flat surface (S) with a surrounding length or a small area around the flat surface (S) with a larger surrounding length or area. . It is believed that a flat surface (S) with a long or larger area around it helps to improve adhesion. On the other hand, it can be achieved by the existence of a recess adjacent to a flat surface (S) with a long or small area around it. Improve degassing.

That is, by satisfying the above-mentioned requirements (1-1) and/or (2-1), a moderate deviation occurs in the contact between the adhesive layer and the adhered surface, and the degassing properties, adhesive properties, appearance, Adhesive sheet with well-balanced improvement of various characteristics such as press processing.

In addition, the "Kurtosis Ku value" specified in the above requirements (1-2) and (2-2) means the peak of the distribution of the surrounding length or area and frequency of a flat surface (S) and the tail of the distribution curve in statistics. The degree of difference between the end curve and the normal distribution curve.

If the kurtosis Ku value = 0, the shape of the distribution curve is almost completely consistent with the normal distribution curve.

If the kurtosis Ku value> 0 (kurtosis Ku is a positive value), the distribution curve has a sharper peak than the normal distribution curve, and the distribution curve has a thicker tail, which means that the tail end of the distribution curve is extended. shape.

If the kurtosis Ku value is less than 0 (kurtosis Ku is a negative value), the distribution curve has a flatter peak than the normal distribution curve, and the distribution curve has a lighter end, which means that the end of the distribution curve has a smaller width. The shape.

Based on the above requirements (1-2) and (2-2), the distribution curve of the surrounding length or area and frequency of the flat surface (S) in the area (D) is shown to have sharper peaks and distributions than the normal distribution curve. The shape of the end of the curve with a wide extension.

Regarding the surrounding length or area of each flat surface (S), the skewness Sk value specified in the above requirement (1-1) or (2-1) is set to> 0, and the above requirement (1-2) Or (2-2) The specified kurtosis Ku value>0 shows that the surrounding length or area and frequency distribution curve of each flat surface (S) shows a shape that is biased towards a smaller number and deviates from the normal distribution.

That is, the distribution of the flat surface (S) is a ratio that can fully ensure the number of flat surfaces (S) with a small surrounding length or area, and the flat surfaces (S) with a large surrounding length or area are also in a minimum ratio The distribution of the above.

Therefore, there is a moderate deviation in the contact between the adhesive layer and the surface to be adhered, and it can be an adhesive sheet with well-balanced improvement in various properties such as degassing, adhesive properties, appearance, and press processing.

In addition, there are a plurality of flat surfaces (convex surfaces) formed by the transfer of the embossed pattern on the surface of the adhesive layer transferred on the embossed pattern of a specific shape made by a general design.

The plurality of flat surfaces formed by the transfer of the embossed pattern also have a variety of sizes according to the design of the embossed pattern. However, since the formation of the embossed pattern is complicated, most of the flat surfaces are fixed in size and shape, or mostly There are repeated flat surfaces of the same shape, in the case where the shape of the flat surface has a certain regularity.

Therefore, the plural flat surfaces formed by the transfer of embossed patterns have regularities in shapes, so the skewness Sk value specified in the above requirements (1-1) and (2-1) rarely exceeds 1.0. The kurtosis Ku specified in the above-mentioned requirements (1-2) and (2-2) rarely exceeds the value specified in each of the requirements.

In addition, in the same aspect of the present invention, the "area of the flat surface" existing in the area (D) can be obtained by using a digital microscope (magnification: 30-100 times) to obtain an image of the area (D) and map the image Image processing (binarization processing) automatic area measurement and measurement.

Then, the standard deviation specified in the above requirements (1) and (2) can be used to calculate the data obtained by free and automatic area measurement using image software (Japan Microsoft Co., Ltd., EXCEL).

In addition, the skewness Sk value of each flat surface (S) specified by the above requirements (1-1) and (2-1) relative to the normal distribution curve of the surrounding length or area and frequency can be obtained by free automatic area measurement The data was calculated based on the following formula (1) using graphics software (Microsoft Corporation of Japan, EXCEL).

[In formula (1), n represents the number of flat surfaces (S), x _i represents the surrounding length or area of each flat surface (S) (i: 1, 2,...n), μ represents each flat surface (S) The average value of the surrounding length or area of the surface (S), s represents the standard deviation of the specimen].

Similarly, the kurtosis Ku value of each flat surface (S) specified by the above requirements (2-1) and (2-2) relative to the surrounding length or the normal distribution curve of area and frequency can be obtained by free automatic area measurement The data was calculated based on the following formula (2) using graphics software (Microsoft Corporation of Japan, EXCEL).

[In formula (2), n represents the number of flat surfaces (S), x _i represents the surrounding length or area of each flat surface (S) (i: 1, 2,...n), μ represents each flat surface (S) The average value of the surrounding length or area of the surface (S), s represents the standard deviation of the specimen].

[About the requirements of the profile (P1)]

The adhesive sheet of the present invention is arbitrarily selected on the surface (α) of the resin layer in an area (P) surrounded by a square of 5 mm on one side, and passes through the two diagonal lines of the square and is opposite to the surface (α). The area (P) on) is on a vertical plane, and at least one of the two cross-sections (P1) obtained by cutting the adhesive sheet in the thickness direction, preferably meets the following requirements (I) and ( II).

‧Requirement (I): On the surface (α) side of the aforementioned section (P1), there is a front The maximum height difference of more than 40% of the total thickness of the resin layer, and the shape of the cut part is a plurality of recesses that are different from each other.

‧Requirement (II): On the surface (α) side of the cross-section (P1), there is a cut portion corresponding to the flat surface existing in the region (P), and it is in contact with the resin layer of the substrate or release material The contacted surface is a slightly parallel flat part.

First, referring to FIG. 4 as appropriate, the process before obtaining the above-mentioned "two cross-sections of the adhesive sheet" will be described.

4 is a diagram for explaining the method of obtaining the "two cross-sections of the adhesive sheet" specified in this specification, and is a perspective view of the adhesive sheet in the same state of the present invention. In FIG. 4, as an example, a perspective view of an adhesive sheet 11a having several layers 12 on a substrate 11 having the same structure as the adhesive sheet 1a, but the recesses and flat surfaces on the surface (α) 12a of the resin layer 12 are shown The record is omitted.

Initially, on the surface (α) 12a of the resin layer 12, an area (P) surrounded by a square 50 of 5 mm on one side is arbitrarily selected. At this time, regarding the selected area (P), the selected position on the surface (α) 12a or the orientation of the square 50 constituting the area (P) is not limited.

Therefore, when the two diagonal lines 51, 52 of the square 50 constituting the area (P) are cut on a plane perpendicular to the surface (α) 12a and the adhesive sheet 11a is cut along the thickness direction A, Obtain 2 sections 61, 62.

That is, the adhesive sheet 11a is cut on a plane perpendicular to the surface (α) 12a along the thickness direction A by passing through the diagonal line 51 When the cross section 61 of the adhesive sheet is obtained.

On the other hand, when the adhesive sheet 11a is cut in a plane perpendicular to the surface (α) 12a along the thickness direction A by passing through the diagonal line 52, a cross section 62 of the adhesive sheet is obtained.

In the present invention, among the two cross-sections 61 and 62 of the adhesive sheet obtained in this way, the one that satisfies the above-mentioned requirements (I) and (II) is denoted as "cross-section (P1)".

In addition, in the same aspect of the present invention, it is preferable that any one of the two cross-sections 61 and 62 corresponds to the cross-section (P1).

In addition, in the present invention, the judgment of whether the two sections 61 and 62 meet the above requirements (I) and (II) and the judgment of whether the section (P1) meets the various requirements described below are based on the use of a scanning electron microscope (magnification: 100~ 1000 times) Obtain the image of the cross section of the object and judge it.

Figure 5 is an example of a schematic diagram of the section (P1) specified in this specification.

The cross section (P1) 60 obtained by the above method is shown in FIG. 5, and on the surface (α) 12a side of the cross section (P1) 60, there are at least a plurality of concave portions 13a and flat portions 14a.

In addition, as shown in FIG. 5, on the surface (α) 12a side of the cross-section (P1) 60, there may be a bulge higher than the flat portion 14a, which does not pass through the surface of the substrate 11 (or release material) that is in contact with the resin layer 12 The straight line e _{β is} slightly parallel to the convex portion 15.

In the aforementioned cross section (P1) 60, as in the aforementioned requirement (I), on the surface (α) 12a side of the aforementioned cross section, there is a maximum height difference of 40% or more of the total thickness of the resin layer 12, and the shape of the cut portion Different complex The number of recesses 13a.

The recess 13a having a maximum height difference of more than 40% of the total thickness of the resin layer 12 is a part that has a greater influence on the degassing property of the adhesive sheet, and plays a role as an air discharge passage.

By making the shapes of the cut portions of the plurality of recesses 13a different from each other in this way, when a force with a fixed directionality is applied to the adhesive sheet before and after the adhesive sheet is attached, all the recesses can be prevented from being deformed in the same way, and the effect can be achieved. The situation where the groove of the role of the air exhaust channel disappears. As a result, it can be an adhesive sheet having very excellent degassing properties.

In addition, based on the above viewpoint, in the aspect of the present invention, the cross-section (P1) 60 preferably includes the shape of the cut portion in the plurality of recesses 13a existing on the surface (α) 12a side defined by the requirement (I) It is an amorphous recess.

In addition, the term "amorphous" here means the same meaning as above.

In the present invention, the judgment of "whether it corresponds to the recess with the maximum height difference greater than 40% of the total thickness of the resin layer 12", the judgment of "whether the shapes of the cut portions of the plural recesses are different from each other", and "whether The judgment that the shape corresponding to the cut part is an amorphous recess is as described above, and is judged by using a digital microscope or a scanning electron microscope to obtain an image of the aforementioned section (P1) 60.

In addition, in the above, the judgment of "whether the shapes of the cut portions of the plural recesses are different from each other" may be determined when, for example, the width, length, and maximum height difference of the two target recesses shown in the above image are different from each other. It was judged that "the shapes of the cut portions of the two recesses are different from each other."

In the aforementioned cross section (P1) 60, as in the aforementioned requirement (II), on the surface (α) 12a side of the aforementioned cross section, there is a cut corresponding to the aforementioned flat surface 14 existing in the region (P) as shown in FIG. 2 The broken portion and the surface contacting the resin layer 12 of the base material or the release material is a flat portion 14a that is slightly parallel.

The flat portion 14a corresponds to a cut surface of the flat surface 14 present on the surface (α), and in the cross section (P1) 60, it becomes a straight line slightly parallel to the surface of the aforementioned substrate or release material.

That is, in the cross-section (P1) 60 shown in FIG. 5, the straight line e _α passing through the flat portion 14 a is slightly parallel to _{the straight line e β} passing through the surface of the substrate 11 in contact with the resin layer 12 and in contact with the resin layer 12. Therefore, as shown in FIG. 4, the flat portion 14a is different from the convex portion 15 that is formed so as to bulge _{upward with respect to the straight line e α and is not slightly parallel to the straight line e β.}

In addition, the term "slightly parallel" in the present invention refers to the straight line e _α passing through the flat portion 14a existing on the surface (α) side of the cross section (P1) and the resin layer passing through the substrate or release material in contact with the resin layer 12 The case where the angle formed by the straight line e _{β of} the contacting surface becomes 0 degrees, of course, also includes the case where the angle formed by it seems to be substantially parallel with a slight slope (for example, the angle formed by the angle is 5 degrees or less , Preferably below 2 degrees).

In addition, from the viewpoint of becoming an adhesive sheet with improved degassing properties and adhesive properties in a more balanced manner, it is preferable that in the aforementioned section (P1) 60, there are a plurality of flat portions 14a on the surface (α) 12a side, and the surface ( α) The position of the plurality of flat portions 14a present on the 12a side does not have periodicity.

Also, the so-called "the position of the flat part does not have periodicity" means that the plural The location of the flat part does not have the same repeating pattern, but is in an irregular (random) state.

In addition, in the cross section (P1) 60, when a plurality of flat portions 14a exist on the surface (α) 12a side of the cross section (P1) 60, each of the plurality of flat portions 14a existing on the surface (α) 12a side reaches the base The distance between the material or the peeling material is preferably the same.

This system 5, the display system may be a plurality of the flat portion 14a by a straight line connecting _e α, _e α linearly straight surface of the contact with the substrate by contacting the sheet with the resin layer or the peeling of the resin layer ₁₂ e β slightly parallel.

In this way, since the positions of the plurality of flat portions 14a in the thickness direction are substantially the same, they can be fully contacted with the bonded surface of the bonded body and contribute to the improvement of adhesion.

In addition, in the present invention, the phrase "the distance between each of the plural flat portions and the aforementioned base material or release material is the same" includes the difference in the distance between the two flat portions to be the object and the base material or release material relative to the average of the distance The value is less than 5% (preferably less than 2%).

In addition, in the same aspect of the present invention, based on the viewpoint of becoming an adhesive sheet with improved degassing properties and adhesion properties in a well-balanced manner, when a plurality of the aforementioned sections (P1) are obtained, there are some on the surface (α) side of each section (P1) The formation position and the formation length of the flat part are preferably different from each other in the obtained complex profile (P1).

That is, if the formation position and the formation length of the flat portion existing on the surface (α) side of the section (P1) are different from those of the other sections (P1), it means that the section (P1) is not the same.

Furthermore, based on the viewpoint of becoming an adhesive sheet with improved degassing properties and adhesive properties in a well-balanced manner, it is better to satisfy at least one of the following requirements (Ia) and (IIa), and more preferably to satisfy the following requirements (Ia) and ( IIa) Both.

‧Requirement (Ia): In the cross-section (P1) 60, the horizontal width (E _α ) of the resin layer 12 on the side of the surface (α) 12a is 100, and the width of the recess 13a on the surface (α) is equal to The total proportion is 10~90.

‧Requirement (IIa): In the cross section (P1) 60, the horizontal width (E _α ) 100 of the resin layer 12 on the side of the surface (α) 12a is occupied by the flat portion 14a on the surface (α) The ratio is 10~90.

_{The "horizontal width (E α} ) of the aforementioned resin layer on the surface (α) side" specified by the requirements (Ia) and (IIa) is _{the length shown by E α} in FIG. 5, for example, if the section (P1) is selected ) The shape of 60 is a rectangle, which corresponds to the horizontal length of the rectangle.

The ratio of the total width of the aforementioned recesses 13a on the surface (α) 12a specified in the requirement (Ia) is 10 to 90, but is preferably 20 to 80, more preferably 25 to 70, and more preferably 30 ~60.

The larger the ratio of the total width of the recesses 13a is, the better the degassing property is, and the smaller the ratio is, and the more the ratio of the flat portion 14a is increased, so the adhesion characteristics are improved.

In addition, as described above, in the present invention, the "recess width" refers to the distance L _{between the two mountain parts (M 1} ) and the mountain part (M _{2) as shown in Fig. 3(a).} Therefore, since the "concave width" becomes the length of a part including the convex section 15, when the convex section 15 is present on the surface (α), the total of the ratio specified by the requirement (Ia) and the ratio specified by the requirement (IIa) is not equal to the horizontal The width in the direction (E _α ) is also "100".

As for requirement (IIa), the ratio of the aforementioned flat portion existing on the surface (α) is 10 to 90, but it is preferably 20 to 80, more preferably 25 to 70, and still more preferably 30 to 60.

The larger the proportion of the flat portion, the better the deaeration performance, and the smaller the proportion, the more the proportion of the recessed portion increases, so the deaeration performance is improved.

In the same aspect of the present invention, the aforementioned recesses are preferably not formed by using a release material having an embossed pattern.

The so-called "recesses formed using a peeling material with embossed patterns" are, for example, the following, which are different from the aforementioned recesses.

‧On the flat surface of the adhesive layer formed from the adhesive composition, press the release sheet with embossed pattern, and the concave portion formed by the transfer of the embossed pattern.

‧Use a peeling sheet with embossed patterns applied to the peeling treatment surface. After coating the adhesive composition on the peeling treatment surface to form an adhesive layer, the recesses exposed on the surface of the adhesive layer when the peeling sheet is removed.

These recesses cause several disadvantages as listed in the problems related to the adhesive sheet described in the aforementioned Patent Document 1.

In the same aspect of the present invention, based on the viewpoint of forming an adhesive sheet that satisfies the aforementioned requirements and a flat surface on the surface (α) of the resin layer, the aforementioned recesses are preferably formed by self-forming of the aforementioned resin layer.

In the present invention, the so-called "self-formation" refers to the phenomenon of forming a naturally disordered shape in the process of self-discipline formation of the resin layer. More specifically, It refers to the phenomenon that the coating film formed from the composition of the forming material of the resin layer is dried to form a natural disordered shape during the process of autonomous formation of the resin layer.

In addition, the shape of the recess formed by the self-forming of the resin can be adjusted to a certain extent by adjusting the drying conditions or the type or content of the components in the composition of the resin layer forming material, but it is different from embossing. The grooves formed by the transfer of the pattern are different, and it can be said that "the same shape cannot be reproduced in fact." Therefore, the recess formed by the self-forming of the resin layer can be said to be amorphous.

In addition, by forming an amorphous recess, the shape of the flat surface also becomes amorphous.

The formation process of the recess formed by the self-forming of the resin layer is considered as follows.

First, in the formation of a coating film made of a composition that becomes a material for forming the resin layer, in the step of drying the coating film, shrinkage stress occurs in the coating film, and the resin bond becomes weaker. Cracks occurred in the coating film. Therefore, it is considered that the resin at the periphery of the cracked portion flows into the space temporarily generated by the crack to form a recess on the surface (α) of the resin layer.

It is considered that after forming two-layer coating films with different resin contents and drying the two-layer coating films at the same time, a difference in shrinkage stress occurs in the coating film during drying, and coating film cracks are likely to occur.

In addition, it is better to appropriately consider the following matters and make adjustments from the viewpoint of easy formation of recesses. It is considered that the formation of the recessed portion becomes easy due to the compound action due to these matters. Incidentally, in order to easily form the recess The preferred aspect of each item is as described in the item described later.

‧The type of resin, constituent monomers, molecular weight, and content contained in the composition of the coating film forming material.

‧The type of crosslinking agent and solvent contained in the composition of the coating film forming material.

‧The viscosity and solid content of the composition of the coating film forming material.

‧The thickness of the formed coating film (in the case of multiple layers, the thickness of each coating film)

‧Drying temperature and drying time of the formed coating film.

In addition, in the formation of the adhesive layer of the general adhesive sheet, the above-mentioned items are set appropriately for the purpose of forming an adhesive layer with a flat surface in most cases.

On the other hand, the present invention sets the above items in a manner intended to form recesses that can help improve the degassing properties of the adhesive sheet, which is completely different from the design method of the adhesive layer of the general adhesive sheet.

The above matters are preferably set appropriately in consideration of the fluidity of the resin contained in the formed coating film, etc.

For example, when fine particles are contained in the composition, by adjusting the viscosity of the coating film formed by the composition containing more fine particles to an appropriate range, the specific fluidity of the fine particles in the coating film can be maintained and the compatibility with other coating films ( The coating film containing more resin) is mixed. By such adjustment, in the coating film containing more resin, there is a tendency for cracks to occur in the horizontal direction, and it is easy to form recesses.

As a result, the ratio of the recesses formed on the surface (α) can be increased, and the ratio of the recesses connected to each other can also be increased, and an adhesive sheet with better degassing properties can be obtained.

In addition, among the above matters, it is preferable to appropriately adjust the type of resin, constituent monomers, molecular weight, and resin content so that the resin contained in the coating film containing a large amount of resin has moderate viscoelasticity.

That is, by making the hardness of the coating film (hardness determined by factors such as the viscoelasticity of the resin and the viscosity of the coating liquid) moderately hard, the shrinkage stress of the resin portion (X) can be increased, and the recesses can be easily formed. The harder the hardness of the coating film, the stronger the shrinkage stress, and the dents are prone to occur, but when the coating film is too hard, the coating suitability decreases. In addition, when the resin elasticity is too high, the adhesive force of the resin layer formed by the coating film tends to decrease. When considering this aspect, it is better to moderately adjust the viscoelasticity of the resin.

In addition, when fine particles are contained in the composition or coating film, it is considered that the degree of bulging of the resin layer thickness caused by the fine particles can be easily adjusted by appropriately adjusting the dispersion state of the fine particles, or the self-forming force of the concave portion can be easily adjusted. (α) A recess is formed on it.

Furthermore, it is preferable to consider the crosslinking speed of the coating film (or the composition of the forming material) to be formed, and to appropriately set the above-mentioned matters.

That is, if the crosslinking speed of the coating film is too fast, the coating film may harden before the recesses are formed. In addition, it also affects the size of cracks and recesses of the coating film.

The crosslinking speed of the coating film can be adjusted by appropriately setting the type of crosslinking agent and the type of solvent in the composition of the forming material, or the drying time and temperature of the coating film.

In addition, when the resin layer is a layer containing a resin-containing resin part (X) and a particle part (Y) made of fine particles, the resin layer formed by the above-mentioned self-forming is shown in Fig. 1(a)~( d) or as shown in Figure 5, the particle part (Y) has a tendency to be distributed in a portion where there are recesses on the surface (α), and the proportion of the particle portion (Y) is smaller than that of other portions.

That is, regarding the resin layer including the resin portion (X) and the particle portion (Y) formed by the self-forming of the resin layer, as shown in FIG. 5, in the aforementioned section (P1) obtained according to the above method, Regarding the distribution of the particle portion (Y), the following trends are seen.

‧The particle part (Y) contained in the resin layer is not uniformly distributed in the horizontal direction.

‧Compared to the concave portion existing on the surface (α), the distribution of the particle portion (Y) in the area (s1) below the concave portion in the thickness direction is at the same level as the area (s1) and on the surface (α) ) The area (s2) with the flat part is relatively small.

This is considered to be due to the movement of fine particles present in the position where the recesses are formed when the recesses are formed on the surface (α) of the resin layer in the process of self-formation of the resin layer.

Hereinafter, each structure of the adhesive sheet of the present invention will be described.

[Substrate]

The substrate used in the aspect of the present invention is not particularly limited, and examples include, for example, a paper substrate, a resin film or sheet, a substrate formed by laminating a paper substrate with a resin, etc., which can be adhered according to the aspect of the present invention. The purpose of the flakes is appropriately selected.

Examples of the paper constituting the paper substrate are thin paper, medium paper, fine paper, etc. Paper, impregnated paper, coated paper, coated paper, sulfuric acid paper, cellophane, etc.

Examples of the resin constituting the resin film or sheet are polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. The ethylene resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyester resins; polystyrene; acrylonitrile-butadiene-styrene Copolymer; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic modified polyurethane; polymethylpentene; polysulfide; polyether ether ketone ; Polyether sulfide; polyphenylene sulfide; polyetherimide, polyimide and other polyimide-based resins; polyimide-based resins; acrylic resins; fluorine-based resins, etc.

As a base material formed by laminating a paper base material with a resin, laminated paper formed by laminating the above-mentioned paper base material with a thermoplastic resin such as polyethylene or the like is exemplified.

Among these substrates, a resin film or sheet is preferred, a film or sheet made of polyester resin is more preferable, and a film or sheet made of polyethylene terephthalate (PET) is more preferable .

In addition, when the adhesive sheet of the present invention is used in applications requiring heat resistance, it is preferably a film or sheet composed of a resin selected from polyethylene naphthalate and polyimide-based resins, and is used when weather resistance is required. In the case of sexual applications, it is preferably a film or sheet composed of a resin selected from polyvinyl chloride, polyvinylidene chloride, acrylic resin and fluororesin.

The thickness of the substrate is appropriately set according to the application of the adhesive sheet of the present invention, but from the viewpoints of handling and economic efficiency, it is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and more preferably 12 to 250 μm. More preferably, it is 15 to 150 μm.

In addition, the base material may further contain various additives such as ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, anti-blocking agents, and colorants.

In addition, the substrate used in the same aspect of the present invention is preferably a non-air-permeable substrate from the viewpoint of improving the burst resistance of the obtained adhesive sheet, and specifically, it is preferred to have a surface of the resin film or sheet. The base material of the metal layer.

Examples of metals contained in the metal layer include metals with metallic luster such as aluminum, tin, chromium, and titanium.

Examples of the method for forming the metal layer include a method of vapor deposition of the above-mentioned metal by a PVD method such as vacuum evaporation, sputtering, ion plating, etc., or a method of attaching a metal foil made of the above-mentioned metal using a general adhesive, etc. However, it is preferably a method of vapor-depositing the above-mentioned metals by the PVD method.

Furthermore, when a resin film or sheet is used as a substrate, based on the viewpoint of improving the adhesion with the resin layer laminated on the resin film or sheet, the surface of the resin film or sheet may be subjected to oxidation or Surface treatment or primer treatment such as embossing method.

Examples of the oxidation method include corona discharge method, plasma discharge treatment, chromic acid treatment (wet), hot air treatment, ozone and ultraviolet irradiation treatment, etc., and examples of the unevenness method include sandblasting, solvent treatment, and the like.

[Peeling material]

As an example of the peeling material in the same state of the present invention, the use of both sides peeled off Treated peeling sheets, peeling sheets with peeling treatment on one side, etc., applying a peeling agent to the base material for the peeling material, etc.

In addition, the peeling treatment surface is preferably a flat peeling material (for example, a peeling material that is not embossed) without forming unevenness.

Examples of the substrate for the release material include the above-mentioned paper substrate, resin film or sheet used as the substrate of the adhesive sheet of the present invention, and a substrate formed by laminating a paper substrate with a resin, etc. .

Examples of release agents include rubber-based elastomers such as silicone resins, olefin-based resins, isoprene-based resins, butadiene-based resins, long-chain alkyl-based resins, alkyd resins, and fluorine-based resins. Wait.

The thickness of the release material is not particularly limited, and is preferably 10 to 200 μm, more preferably 25 to 170 μm, and still more preferably 35 to 80 μm.

[Resin layer]

As shown in FIG. 1, the resin layer 12 of the adhesive sheet of the present invention preferably includes a resin portion (X) containing resin and a particle portion (Y) made of fine particles.

The resin part (X) represents a part containing components other than the fine particles contained in the resin layer. That is, the resin layer contains not only resin, but also components other than fine particles such as adhesion imparting agents, crosslinking agents, and general-purpose additives are included in the "resin part (X)".

On the other hand, the particle part (Y) means a part formed by fine particles contained in the resin layer.

Due to the particle part (Y) contained in the resin layer, the adhesion can be improved After the shape retention, the resulting adhesive sheet can effectively suppress the occurrence of bursting when used at high temperatures.

As the composition of the distribution of the resin part (X) and the particle part (Y) in the resin layer 12, the resin part (X) and the particle part (Y) can be roughly evenly distributed, or it can be divided into a part mainly composed of a resin part The composition of the part formed by (X) and the part mainly formed by the particle part (Y).

In addition to the resin portion (X) and the particle portion (Y), the resin layer included in the adhesive sheet of the present invention preferably further has a void portion (Z). Due to the void portion (Z) in the resin layer, the burst resistance of the adhesive sheet can be improved.

The void portion (Z) also includes voids existing between the fine particles, or voids existing in the secondary particles when the particles are secondary particles.

In addition, when the resin layer has a multilayer structure, even if there is a void portion (Z) during the formation of the resin layer or immediately after the formation, the resin portion (X) flows into the void portion (Z) and the void disappears and becomes a void-free portion. (Z) The situation of the resin layer.

However, even if the void portion (Z) that exists in the resin layer for a short period of time disappears, the adhesive sheet of the present invention has a concave portion on the surface (α) of the resin layer, so the outgassing performance is good, and because of the resin Since the layer has a particle portion (Y), it is also excellent in burst resistance.

In addition, the shear storage elastic modulus at 100°C of the resin layer of the adhesive sheet of the present invention is preferably 9.0×10 ³ Pa based on the viewpoint that the outgassing property and burst resistance of the adhesive sheet are improved. Above, it is more preferably 1.0×10 ⁴ Pa or more, and still more preferably 2.0×10 ⁴ Pa or more.

In addition, in the present invention, the shear storage elastic modulus of the resin layer at 100°C means the measurement obtained by measuring at a frequency of 1 Hz using a viscoelasticity measuring device (for example, manufactured by Rheometrics, with the device name "DYNAMIC ANALYZER RAD II") value.

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

The adhesive sheet of the present invention has adhesiveness at least on the surface (α) of the resin layer opposite to the side where the substrate or release material is provided, but on the surface of the resin layer on the side where the substrate or release material is provided (β) can also be adhesive.

The adhesive force of the surface (α) of the resin layer of the adhesive sheet of the present invention is preferably 0.5N/25mm or more, more preferably 2.0N/25mm or more, still more preferably 3.0N/25mm or more, and still more preferably It is 4.0N/25mm or more, and more preferably 7.0N/25mm or more.

And when the surface (β) of the resin layer also has adhesiveness, the adhesive force of the surface (β) preferably falls within the above-mentioned range.

In addition, the value of the adhesive force of the adhesive sheet means the value measured by the method described in the examples.

<Multilayer structure of resin layer>

The resin layer may also be a multilayer structure composed of two or more layers.

As the resin layer of such a multilayer structure, for example, the adhesive as shown in Figure 1 Like the attached sheet 1a, etc., from the side where the base material or release material is provided, the layer (Xβ) mainly containing the resin portion (X), the layer (Y1) containing 15% by mass or more of the particle portion (Y), and the layer (Y1) mainly containing The layer (Xα) of the resin part (X) is laminated in the order of a multilayer structure.

In addition, in the structure of the multilayer structure of the resin layer, it can be a mixed layer state in which the boundary of the two laminated layers cannot be distinguished.

That is, it can also be the resin layer 12 of the adhesive sheet 1a of FIG. 1, the boundary between the layer (Xβ) and the layer (Y1) and/or the boundary between the layer (Y1) and the layer (Xα) cannot be distinguished from the mixed layer constitute.

Hereinafter, the resin layer 12 composed of three layers (Xβ), layer (Y1), and layer (Xα) included in the adhesive sheet 1a of FIG. 1 is taken as an example to describe the structure of the resin layer of the multilayer structure.

The layer (Xβ) and the layer (Xα) are layers mainly containing the resin part (X), but may also contain the particle part (Y). However, the content of the particle part (Y) in the layer (Xβ) and the layer (Xα) is less than 15% by mass and less than the total mass (100% by mass) of the layer (Xβ) or the layer (Xα), respectively. The resin content in layer (Xβ) or layer (Xα).

That is, from the viewpoint of the content of the particle portion (Y), the layer (Xβ) and the layer (Xα) are different from the layer (Y1).

In addition, the layer (Xβ) and the layer (Xα) may further have the aforementioned void portion (Z) in addition to the resin portion (X) and the particle portion (Y).

The content of the resin part (X) in the layer (Xβ) and the layer (Xα) is independent of the total mass (100 mass%) of the layer (Xβ) or the layer (Xα), usually exceeding 85% by mass, preferably 87 ~100% by mass, better 90~100 quality %, more preferably 95-100% by mass, still more preferably 100% by mass.

In addition, the above-mentioned "content of resin part (X)" means fine particles of resin, adhesive agent, crosslinking agent, general additives, etc. which constitute the layer (Xβ) or the resin part (X) contained in the layer (Xα) The total content of other ingredients.

The content of fine particles in the particle portion (Y) of the constituent layer (Xβ) and layer (Xα) is less than 15% by mass independently of the total mass (100% by mass) of the layer (Xβ) or layer (Xα), preferably It is 0-13 mass%, more preferably 0-10 mass%, still more preferably 0-5 mass%, still more preferably 0 mass%.

In addition, in the present invention, "the content of fine particles in the layer (Xβ) and layer (Xα)" can also be regarded as the total amount (100% by mass (but 100% by mass) of the resin composition of the material forming the layer (Xβ) and layer (Xα) Except for the dilution solvent)) the content of fine particles.

The resin content in the layer (Xα) is generally 30-100% by mass relative to the total mass (100% by mass) of the layer (Xα), preferably 40-100% by mass, more preferably 50-100% by mass, It is more preferably 60 to 100% by mass.

On the other hand, as the resin content in the layer (Xβ), the total mass (100% by mass) of the layer (Xβ) is usually 50-100% by mass, preferably 65-100% by mass, more preferably 75%. 100% by mass, more preferably 85-100% by mass.

In addition, in the present invention, "the resin content in the layer (Xβ) and the layer (Xα)" can also be regarded as the total amount (100% by mass (but 100% by mass) of the resin composition of the material forming the layer (Xβ) or layer (Xα) The resin content in )) except for the dilution solvent.

The layer (Y1) may also be a layer composed of only the particle part (Y), or a layer including the resin part (X) together with the particle part (Y), or It is a layer with a void portion (Z).

The content of fine particles in the particle portion (Y) of the constituent layer (Y1) is 15% by mass or more relative to the total mass (100% by mass) of the layer (Y1), preferably 20-100% by mass, more preferably 25-90% by mass %, more preferably 30 to 85% by mass, still more preferably 35 to 80% by mass.

The resin content in the constituent layer (Y1) is usually 0-85% by mass relative to the total mass (100% by mass) of the layer (Y1), preferably 1 to 80% by mass, more preferably 5-75% by mass, and more It is preferably 10 to 70% by mass, and still more preferably 20 to 65% by mass.

In addition, in the present invention, "the content of fine particles in the layer (Y1)" and "the content of the resin in the layer (Y1)" can also be regarded as the total amount of the resin composition (100% by mass ( Except for the dilution solvent)) the fine particles or resin content.

In the same aspect of the present invention, the layer (Xα) is preferably a layer formed of a composition (xα) containing a resin and having a fine particle content of less than 15% by mass.

Similarly, the layer (Xβ) is also preferably a layer formed of a composition (xβ) containing a resin and having a fine particle content of less than 15% by mass.

In addition, the layer (Y1) is preferably a layer formed of a composition (y) containing 15% by mass or more of fine particles.

In addition, the preferable aspects (contained components, content, etc.) of the composition (xα), the composition (xβ), and the composition (y1) will be described later.

<Resin part (X)>

The resin part (X) constituting the resin layer contains the micro The component part other than particles is different from the particle part (Y) in this respect.

The resin part (X) may contain an adhesion imparting agent, a crosslinking agent, general additives, etc. together with the resin.

The resin content in the resin part (X) relative to the total mass (100% by mass) of the resin part (X) is usually 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 100% by mass or less, more preferably 99.9% by mass or less.

Furthermore, in the present invention, the value of the resin content in the resin composition of the resin part (X) as a forming material can also be regarded as the "resin content in the resin part (X)".

As the aforementioned resin contained in the resin portion (X), it is preferable to contain an adhesive resin from the viewpoint of exhibiting adhesiveness to the surface (α) of the formed resin layer.

In particular, as in the adhesive sheet 1a of Figure 1(a), the resin layer has a layer (Xβ), layer (Y1), and layer (Xα) laminated in the order from the side where the base material or release material is provided. In the case of a multilayer structure, it is preferable that at least the layer (Xα) contains an adhesive resin based on the above-mentioned viewpoint.

In addition, from the viewpoint of the structure of the double-sided adhesive sheet and the viewpoint of improving the adhesion to the substrate, it is preferable that at least the layer (Xα) and the layer (Xβ) contain an adhesive resin.

Examples of the adhesive resin include acrylic resins, urethane resins, rubber resins, silicone resins, and the like.

Among these adhesive resins, acrylic resins are preferably included from the viewpoint that the adhesive properties and weather resistance are good, and the recesses are easily formed on the surface (α) of the resin layer.

The content of the acrylic resin is preferably from 25 to 100% by mass, more preferably from 50 to 100% by mass, and still more preferably from 70 to the total amount of the aforementioned resin (100% by mass) contained in the resin part (X) 100% by mass, more preferably 80-100% by mass, and still better still be 100% by mass.

In addition, from the viewpoint of easy formation of recesses on the surface (α) of the resin layer, the resin portion (X) preferably contains a resin having a functional group, and more preferably contains an acrylic resin having a functional group.

In particular, like the adhesive sheet 1a in Figure 1(a), the resin layer has a layer (Xβ), layer (Y1), and layer (Xα) laminated in the order from the side where the base material or release material is provided. In the case of a multilayer structure, based on the above-mentioned viewpoint, it is preferable that at least the layer (Y1) contains a resin having a functional group.

The functional group is a group that becomes the starting point of crosslinking with the crosslinking agent, and examples thereof include a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a cyano group, a ketone group, an alkoxysilyl group, etc., but a carboxyl group is preferred.

The resin part (X) preferably contains a resin having the aforementioned functional group and at the same time further contains a crosslinking agent. In particular, when the resin layer is the above-mentioned multilayer structure, it is preferable that at least the layer (Y1) contains the resin having the aforementioned functional group and further contains a crosslinking agent.

Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents, and the like.

Examples of isocyanate-based crosslinking agents are toluene diisocyanate Aromatic polyisocyanates such as esters, diphenylmethane diisocyanate and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic rings of isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Formula polyisocyanate; and uret, isocyanurate and low-molecular-weight compounds containing active hydrogen (ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc.) The adduct of the reactant; etc.

Examples of epoxy crosslinking agents include, for example, ethylene glycol diglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'- Tetraglycidyl-m-xylene diamine, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidyl amine, etc.

As an aziridine-based crosslinking agent, for example, diphenylmethane-4,4'-bis(1-aziridine carboxamide), trimethylolpropane tris-β-aziridine propionate, tetrakis Hydroxymethylmethane tris-β-aziridine propionate, toluene-2,4-bis(1-aziridine carboxamide), triethylene melamine, bis-meta-xylylene-1-( 2-methylaziridine), tri-1-(2-methylaziridine)phosphine, trimethylolpropane, tris-β-(2-methylaziridine)propionate and the like.

An example of a metal chelate crosslinking agent is a chelate compound in which the metal atom is aluminum, zirconium, titanium, zinc, iron, tin, etc. However, from the viewpoint of easy formation of recesses on the surface (α) of the resin layer, aluminum is preferred Chelate is a crosslinking agent.

Examples of aluminum chelate crosslinking agents include, for example, aluminum diisopropoxide monooleyl acetate, monoisopropoxide aluminum dioleyl acetate, monoisopropoxide Aluminum Oxide Monooleate Monoethyl Acetate, Diisopropoxy Aluminum Monolauryl Acetate, Diisopropoxide Aluminum Monostearyl Acetate, Diisopropyl Aluminum oxide monoisostearyl acetyl acetate and so on.

Moreover, these crosslinking agents can be used individually or in combination of 2 or more types.

Among them, the resin part (X) preferably contains one or more selected from the group consisting of a metal chelate-based crosslinking agent and an epoxy-based crosslinking agent, based on the viewpoint that it is easy to form recesses on the surface (α) of the resin layer. It preferably contains a metal chelate crosslinking agent, and more preferably contains an aluminum chelate crosslinking agent.

The content of the crosslinking agent in the resin part (X) is preferably 0.01-15 parts by mass, more preferably 0.1-10 parts by mass relative to 100 parts by mass of the resin having functional groups contained in the resin part (X), and More preferably, it is 0.3 to 7.0 parts by mass.

Furthermore, as an aspect of the present invention, the resin portion (X) preferably contains both a metal chelate-based crosslinking agent and an epoxy-based crosslinking agent from the viewpoint that it is easy to form recesses on the surface (α) of the resin layer.

When the resin part (X) contains both a metal chelate crosslinking agent and an epoxy crosslinking agent, based on the above point of view, the metal chelate crosslinking agent and epoxy crosslinking agent in the resin part (X) The content ratio [metal chelate crosslinking agent/epoxy crosslinking agent] is calculated by mass ratio, preferably 10/90~99.5/0.5, more preferably 50/50~99.0/1.0, and still more It is 65/35~98.5/1.5, more preferably 75/25~98.0/2.0.

From the viewpoint of improving the adhesive properties of the surface (α), the resin part (X) preferably contains an adhesive resin and further contains an adhesive imparting agent. In particular, when the resin layer is the above-mentioned multilayer structure, the layer (Xα) preferably contains an adhesive resin and an adhesive imparting agent.

In addition, the adhesive imparting agent used in the present invention refers to a component that assists in improving the adhesive force of the adhesive resin. The mass average molecular weight (Mw) of oligomers usually less than 10,000 is different from the above-mentioned adhesive resin.

The mass average molecular weight (Mw) of the adhesion imparting agent is preferably 400 to 8000, more preferably 5000 to 5000, and still more preferably 800 to 3500.

Examples of adhesion-imparting agents include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins in which the rosin resins are hydrogenated; terpene resins, aromatic modified terpene resins, Terpene resins such as terpene phenol resins; hydrogenated terpene resins obtained by hydrogenation of these terpene resins; styrene monomers such as α-methylstyrene or β-methylstyrene and aliphatic Styrenic resins obtained by copolymerization of monomers; hydrogenated styrenic resins obtained by hydrogenation of these styrenic resins; pentene, isoprene, piperine, 1,3 produced by thermal decomposition of naphtha -C5 series petroleum resin obtained by copolymerization of C5 fractions of pentadiene and hydrogenated petroleum resin of the C5 series petroleum resin; obtained by copolymerization of C9 fractions such as indene and vinyl toluene produced by thermal decomposition of naphtha The C9 series petroleum resin and the hydrogenated petroleum resin of the C9 series petroleum resin; etc.

The adhesion-imparting agent used in the present invention may be used alone or in combination of two or more types with different softening points or structures.

The softening point of the adhesion imparting agent is preferably 80°C or higher, more preferably 80 to 180°C, still more preferably 83 to 170°C, still more preferably 85 to 150°C.

In the present invention, the "softening point" of the adhesion imparting agent means according to JIS Value measured by K 2531.

In addition, when two or more types of plural adhesive imparting agents are used, the weighted average of the softening points of the plural adhesive imparting agents preferably falls within the above-mentioned range.

When the resin part (X) contains an adhesion-imparting agent, the content of the adhesion-imparting agent is preferably 1 part by mass or more, more preferably 1 to 200 parts by mass relative to 100 parts by mass of the adhesive resin contained in the resin part (X) , More preferably 3~150 parts by mass, still more preferably 5~90 parts by mass.

In addition, the resin part (X) may contain general additives other than the above-mentioned crosslinking agent or adhesion imparting agent.

Examples of general additives are, for example, antioxidants, softeners (plasticizers), rust inhibitors, pigments, dyes, retarders, reaction accelerators, ultraviolet absorbers, and the like.

Moreover, these general-purpose additives can be used individually or in combination of 2 or more types, respectively.

When these general additives are contained, the content of each general additive relative to 100 parts by mass of the resin is preferably 0.0001-60 parts by mass, more preferably 0.001-50 parts by mass.

The aforementioned resin contained in the resin part (X) may be only one type, or may be used in combination of two or more types.

The material for forming the resin portion (X) of the resin layer of the adhesive sheet of the present invention is preferably an adhesive containing an adhesive resin having a functional group, and more preferably an acrylic resin having a functional group (A)( Hereinafter, it is also only referred to as "acrylic resin (A)") acrylic adhesive, and more preferably acrylic resin containing functional group acrylic resin (A) and crosslinking agent (B) Department of adhesive.

The acrylic adhesive may be either solvent type or emulsion type.

The following describes the above-mentioned acrylic adhesive which is preferable as a material for forming the resin portion (X).

Examples of the acrylic resin (A) contained in the acrylic adhesive include, for example, polymers having structural units derived from alkyl (meth)acrylates having linear or branched alkyl groups, and polymers derived from having cyclic (Meth)acrylic acid esters of the structure of the polymer, etc.

The mass average molecular weight (Mw) of the acrylic resin (A) is preferably 50,000 to 1.5 million, more preferably 150,000 to 1.3 million, still more preferably 250,000 to 1.1 million, still more preferably 350,000 to 90 Million.

The acrylic resin (A) preferably includes a structure having an alkyl (meth)acrylate (a1') derived from an alkyl group having 1 to 18 carbon atoms (hereinafter also referred to as "monomer (a1')") The unit (a1) and the acrylic copolymer (A1) derived from the structural unit (a2) of the functional group-containing monomer (a2') (hereinafter also referred to as "monomer (a2')"), more preferably acrylic Copolymer (A1).

The content of the acrylic copolymer (A1) is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass relative to the total amount (100% by mass) of the acrylic resin (A) in the acrylic adhesive , More preferably 80-100% by mass, still more preferably 90-100% by mass.

In addition, the copolymerization form 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 the carbon number of the alkyl group of the monomer (a1’), based on increasing From the viewpoint of adhesive properties, 4-12 are preferable, 4-8 are more preferable, and 4-6 are still more preferable.

As the monomer (a1'), for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, etc.

Among these, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate is more preferred.

The content of the constituent unit (a1) is preferably from 50 to 99.5% by mass, more preferably from 60 to 99% by mass, and more preferably from 70 to all constituent units (100% by mass) of the acrylic copolymer (A1) ~95% by mass, still more preferably 80~93% by mass.

As the monomer (a2'), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an epoxy group-containing monomer, an amine group-containing monomer, a cyano group-containing monomer, a ketone group-containing monomer, and an alkoxy group-containing monomer Silane-based monomers, etc.

Among these, a carboxyl group-containing monomer is more preferable.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, fumaric acid, and itaconic acid, and (meth)acrylic acid is preferred.

The content of the constituent unit (a2) is preferably from 0.5 to 50% by mass, more preferably from 1 to 40% by mass, still more preferably 5 relative to the total constituent units (100% by mass) of the acrylic copolymer (A1) ~30% by mass, still more preferably 7-20% by mass.

In addition, the acrylic copolymer (A1) may contain a structural unit (a3) derived from a monomer (a3') other than the above-mentioned monomers (a1') and (a2').

Examples of other monomers (a3') include, for example, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth) ) (Meth) acrylate, vinyl acetate, acrylonitrile with cyclic structure such as dioxopentenyl acrylate, dicyclopentyloxyethyl (meth)acrylate, imine (meth)acrylate, etc. , Styrene, etc.

The content of the constituent unit (a3) is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, and still more preferably 0 relative to the total constituent unit (100% by mass) of the acrylic copolymer (A1) ~10% by mass, more preferably 0~5% by mass.

In addition, the above-mentioned monomers (a1') to (a3') may be used alone or in combination of two or more kinds.

The method of synthesizing the acrylic copolymer (A1) component is not particularly limited. For example, it can be achieved by dissolving the raw material monomers in a solvent, solution polymerization in the presence of a polymerization initiator, chain transfer agent, etc., or It is produced by the method of aqueous emulsion polymerization using raw material monomers in the presence of emulsifiers, polymerization initiators, chain transfer agents, dispersants, etc.

The crosslinking agent (B) contained in the aforementioned acrylic adhesive is exemplified by the above, but from the viewpoint that the adhesive properties become better and the recesses are easily formed on the surface (α) of the resin layer, it is preferable to contain a metal chelate One or more of the material-based crosslinking agent and the epoxy-based crosslinking agent, preferably contains a metal chelate-based crosslinking agent, and more preferably contains an aluminum chelate-based crosslinking agent.

In addition, as an aspect of the present invention, based on the viewpoint of improving the shape maintenance of the plurality of recesses existing on the resin layer surface (α), as the crosslinking agent (B), it is preferable to contain a metal chelate crosslinking agent and a ring together. Oxygen-based crosslinking agent.

The content of the crosslinking agent (B) is preferably 0.01-15 parts by mass, more preferably 0.1-10 parts by mass, and still more preferably, relative to 100 parts by mass of the acrylic resin (A) in the aforementioned acrylic adhesive 0.3 to 7.0 parts by mass.

When a metal chelate crosslinking agent and an epoxy crosslinking agent are used together, the content ratio of the metal chelate crosslinking agent to the epoxy crosslinking agent is "Metal chelate crosslinking agent/epoxy crosslinking agent". "Crosslinking agent" is calculated by mass ratio, preferably 10/90~99.5/0.5, more preferably 50/50~99.0/1.0, still more preferably 65/35~98.5/1.5, still more preferably 75/25 ~98.0/2.0.

The acrylic adhesive used in the same aspect of the present invention may also contain general additives within a range that does not impair the effects of the present invention. Examples of general additives are those described above, and the content of the general additives is also the same as described above.

In addition, the acrylic adhesive used in the same aspect of the present invention preferably further contains an adhesive imparting agent from the viewpoint of further improving the adhesive properties of the surface (α). Examples of the adhesion-imparting agent are those described above, and the content of the adhesion-imparting agent is also as described above.

The acrylic adhesive used in the same aspect of the present invention may contain adhesive resins other than the acrylic resin (A) (for example, urethane-based resins, rubber-based adhesives) within the range that does not impair the effects of the present invention. Resin, silicone resin, etc.).

The content of acrylic resin (A) in the acrylic adhesive is preferably 50-100% by mass, more preferably 70-100 relative to the total amount of adhesive resin (100% by mass) contained in the acrylic adhesive % By mass, more preferably 80-100% by mass, still more preferably 100% by mass.

<Particle Part (Y)>

The resin layer of the adhesive sheet of the present invention preferably contains a particle portion (Y) made of fine particles.

The average particle size of the fine particles, based on the viewpoint of improving the outgassing and burst resistance of the adhesive sheet and the viewpoint of easy formation of recesses and flat surfaces on the resin layer surface (α), is preferably 0.01-100μm, more preferably 0.05~ 25μm, more preferably 0.1-10μm.

The fine particles used in the same state of the present invention are not particularly limited, and examples include inorganic particles such as silica particles, metal oxide particles, barium sulfate, calcium carbonate, magnesium carbonate, glass beads, bentonite, etc., or organic particles such as acrylic beads. Particles and so on.

Among these fine particles, one or more selected from the group consisting of silica particles, metal oxide particles, and bentonite are preferred, and silica particles are more preferred.

The silicon dioxide particles used in the same state of the present invention can be any of dry silicon dioxide particles and wet silicon dioxide particles.

Moreover, the silica particles used in the same state of the present invention can also be organically modified silica particles surface-modified with organic compounds with reactive functional groups, or inorganic compounds surface-treated with inorganic compounds such as sodium aluminate or sodium hydroxide. Modified silica, organic-inorganic modified silica surface-treated with these organic compounds and inorganic compounds, organic-inorganic modified silica surface-treated with organic-inorganic hybrid materials such as silane coupling agent, etc.

In addition, the silica particles may be a mixture of two or more kinds.

The mass concentration of silicon dioxide in silicon dioxide particles, relative to Based on the total amount of silicon dioxide particles (100% by mass), it is preferably from 70 to 100% by mass, more preferably from 85 to 100% by mass, and still more preferably from 90 to 100% by mass.

In addition, the volume average secondary particle size of the silicon dioxide particles used in the same state of the present invention is based on the viewpoint of improving the outgassing and burst resistance of the adhesive sheet, and on the basis that it is easy to form recesses and flat surfaces on the surface (α) of the resin layer From this viewpoint, it is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and still more preferably 1.5 to 5 μm.

In addition, in the present invention, the value of the volume average secondary particle size of the silica particles is a value obtained by measuring the particle size distribution by the Coulter counting method using a Multisizer 3 machine or the like.

As the metal oxide particles, for example, metal oxides selected from titanium oxide, aluminum oxide, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide, and composite oxides thereof The formed particles, etc. also include sol particles formed from these oxidized metals.

Examples of bentonite include montmorillonite, aluminum bentonite, saponite, saponite, talcite, nontronite, and zinc bentonite.

The quality retention rate of the resin layer of the adhesive sheet of the present invention after heating at 800°C for 30 minutes is preferably from 3 to 90% by mass, more preferably from 5 to 80% by mass, more preferably from 7 to 70% by mass, It is more preferably 9-60% by mass.

This mass retention rate can be regarded as representing the content (mass %) of fine particles contained in the resin layer.

If the mass retention rate is 3% by mass or more, it can become degassing and Adhesive sheet with excellent burst resistance. In addition, during the production of the adhesive sheet of the present invention, it is easy to form recesses on the surface (α) of the resin layer.

On the other hand, if the mass retention ratio is 90% by mass or less, it can be an adhesive sheet with high film strength of the resin layer and excellent water resistance or chemical resistance. In addition, during the production of the adhesive sheet of the present invention, it is easy to form a flat surface on the surface (α) of the resin layer.

[Method of manufacturing adhesive sheet]

Next, the manufacturing method of the adhesive sheet of the present invention will be described.

The manufacturing method of the adhesive sheet of the present invention is not particularly limited, but from the viewpoint of productivity and the viewpoint of easy formation of recesses and flat surfaces on the resin layer surface (α), it is preferable to have at least the following steps (1 ) And (2) method.

Step (1): forming a coating film (x') composed of a composition (x) containing a resin and a content of less than 15% by mass of fine particles, and a composition (y) composed of a composition (y) containing 15% by mass or more of fine particles The step of coating film (y'); step (2): the step of drying the coating film (x') and the coating film (y') formed in step (1) at the same time.

<Step (1)>

Step (1) is to form a coating film (x') composed of a composition (x) containing resin and a content of less than 15% by mass of fine particles, and a composition (y) composed of a composition (y) containing 15% by mass or more of fine particles The step of coating (y').

The composition (x) is the material forming the resin part (X), and preferably contains at the same time The above-mentioned resin and crosslinking agent may further contain an adhesion-imparting agent or the above-mentioned general-purpose additives.

In addition, the composition (y) serves as a material for forming the particle portion (Y), but may further contain a resin, a crosslinking agent, an adhesion imparting agent, and the aforementioned general-purpose additives. The composition (y) containing components other than the fine particles of the resin and the like becomes a material for forming the particle part (Y) and also becomes a material for forming the resin part (X).

(Composition (x))

The resin contained in the composition (x) is exemplified by the resin constituting the above-mentioned resin part (X), preferably an adhesive resin having a functional group, more preferably an acrylic resin (A) having the above-mentioned functional group, and more Preferably, it is the above-mentioned acrylic copolymer (A1).

The resin content in the composition (x) is generally 30% by mass or more, preferably 40% by mass or more, more preferably 40% by mass or more relative to the total amount of the composition (x) (100% by mass (except for the dilution solvent)) 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 95% by mass or less.

Furthermore, as the crosslinking agent contained in the composition (x), for example, the crosslinking agent contained in the above-mentioned resin part (X), but the composition (x) preferably contains a crosslinking agent selected from the group consisting of metal chelate One or more of epoxy-based cross-linking agents, preferably containing a metal chelate-based cross-linking agent.

Furthermore, as an aspect of the present invention, it is based on improving the presence of the resin layer From the viewpoint of the shape maintainability of the plurality of recesses on the surface (α), the composition (x) preferably contains both a metal chelate-based crosslinking agent and an epoxy-based crosslinking agent.

When the composition (x) contains both the metal chelate crosslinking agent and the 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 crosslinking agent] in terms of mass ratio, preferably 10/90~99.5/0.5, more preferably 50/50~99.0/1.0, more preferably 65/35~98.5 /1.5, even better 75/25~98.0/2.0.

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 0.3 to 7.0 parts by mass relative to 100 parts by mass of the resin contained in the composition (x).

The composition (x) is preferably an acrylic adhesive containing an acrylic resin (A) having the above functional group and a crosslinking agent (B), and more preferably contains the above acrylic copolymer (A1) and crosslinking Acrylic adhesive of agent (B). In addition, the acrylic adhesive may further contain an adhesive imparting agent or a general-purpose additive.

In addition, the details of the above-mentioned acrylic adhesive are as described above.

The composition (x) may contain the above-mentioned fine particles.

However, the content of the fine particles in the composition (x) is less than 15% by mass, and is less than the resin content in the composition (x).

The content of the fine particles in the specific composition (x) is less than 15% by mass relative to the total amount of the composition (x) (100% by mass (except for the dilution solvent)), preferably 0-13% by mass, more preferably 0-10% by mass, more preferably 0-5% by mass, still more preferably 0% by mass.

(Composition (y))

The composition (y) is the material forming the particle portion (Y) and contains at least 15% by mass or more of the above-mentioned fine particles. However, from the viewpoint of the dispersibility of the fine particles, it is better to contain the resin together with the fine particles, and more preferably together with the resin Contains crosslinking agent. In addition, the composition (y) may further contain an adhesion-imparting agent or general-purpose additives.

In addition, components other than the fine particles contained in the composition (y) (resin, crosslinking agent, adhesion-imparting agent, and general additives) become the material for forming the resin portion (X).

The fine particles contained in the composition (y) are exemplified by the above, but based on the viewpoint that the void portion (Z) formed in the resin layer becomes an adhesive sheet with improved burst resistance, it is preferably selected from silicon dioxide particles, One or more of oxidized metal particles and bentonite.

The content of fine particles in the composition (y) is based on the viewpoint that it is easy to form amorphous recesses and flat surfaces formed by the formation of the resin layer on the surface (α) of the resin layer, relative to the total amount of the composition (y) (100% by mass (except for the dilution solvent)), 15% by mass or more, preferably 20-100% by mass, more preferably 25-90% by mass, still more preferably 30-85% by mass, still more preferably 35-80 quality%.

As the resin contained in the composition (y), the same resin as the resin contained in the above-mentioned composition (x) is exemplified, but it is preferable to contain the same resin as the composition (x). Moreover, these resins can be used individually or in combination of 2 or more types.

In addition, as a more specific resin contained in the composition (y), it is preferable to have The resin having a functional group is more preferably an acrylic resin (A) having the above-mentioned functional group, and still more preferably the above-mentioned acrylic copolymer (A1).

The resin content in the composition (y), relative to the total amount of the composition (y) (100% by mass (except for the dilution solvent)), is usually 0-85% by mass, preferably 1-80% by mass, more preferably 5 ~75% by mass, more preferably 10~70% by mass, still more preferably 20~65% by mass.

In addition, examples of the crosslinking agent contained in the composition (y) are the same as the crosslinking agent contained in the above-mentioned resin portion (X). Among these, the composition (y) preferably contains one or more selected from a metal chelate-based crosslinking agent and an epoxy-based crosslinking agent, and more preferably contains a metal chelate-based crosslinking agent. Furthermore, as an aspect of the present invention, the composition (y) preferably contains both a metal chelate-based crosslinking agent and an epoxy-based crosslinking agent.

In addition, when the composition (y) contains both the metal chelate crosslinking agent and the epoxy crosslinking agent, the metal chelate crosslinking agent and the epoxy crosslinking agent in the composition (y) are contained The range of the ratio (mass ratio) is the same as that of the above-mentioned composition (x).

The content of the crosslinking agent in the composition (y) is preferably 0.01-15 parts by mass, more preferably 0.1-10 parts by mass, and still more preferably 0.3-7.0 with respect to 100 parts by mass of the resin contained in the composition (y) Mass parts.

(Method of forming coating film (x’) and (y’))

Moreover, when forming a coating film, in order to make it easy to form a coating film, it is preferable to mix|blend a solvent in the composition (x), (y), and make it into the solution form of a composition.

Examples of such a solvent include water, organic solvents, and the like.

As the organic solvent, for example, toluene, ethyl acetate, butyl acetate Ester, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, tertiary butanol, second butanol, acetone, cyclohexanone, n-hexane, cyclohexane, etc. Moreover, these solvents can be used individually or in combination of 2 or more types.

The laminating order of the coating films (x') and (y') formed in this step is not particularly limited, but it is preferably formed by laminating the coating film (x') on the coating film (y').

The method of forming the coating film (x') and (y') can be a method of successively forming the coating film (x') on the coating film (y') after the coating film (y') is formed, and is based on the viewpoint of productivity , The method of forming the coating film (y') and the coating film (x') by simultaneous coating with a multi-layer coater is also possible.

Examples of coaters used in the successive formation are, for example, spin coaters, spray coaters, bar coaters, knife coaters, roll coaters, knife roll coaters, blade coaters, gravure coaters, etc. Cloth device, curtain flow coater, die nozzle coater, etc.

Examples of the coater used for simultaneous coating of the multi-layer coater are, for example, a curtain coater, a die nozzle coater, etc. Among these, the die nozzle coater is preferred from the viewpoint of operability.

In addition, in this step (1), after at least one of the coating film (x') and the coating film (y') is formed, before proceeding to step (2), it is also possible to apply a treatment that does not cause the coating film to undergo a hardening reaction. Degree of pre-drying treatment.

In this step (1), the drying temperature during the pre-drying treatment is usually set appropriately within a temperature range that does not harden the formed coating film, but preferably does not reach the drying temperature in step (2). The specific drying temperature specified as the "drying temperature not reached step (2)" is preferably 10~45°C, more It is preferably 10 to 34°C, and more 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 in step (1).

In this step, by drying the formed coating film (x') and coating film (y') at the same time, a resin layer containing the resin part (X) and the particle part (Y) is formed, and at the same time on the surface of the resin layer ( α) Form a plurality of recesses and flat surfaces.

The drying temperature in this step is preferably 35 to 200°C, more preferably 60 to 180°C, and still more preferably 70 to 160°C from the viewpoint of easy formation of recesses and flat surfaces on the resin layer surface (α). More preferably, it is 80 to 140°C.

If the drying temperature is 35°C or higher, an adhesive sheet with good degassing properties can be obtained. On the other hand, if the drying temperature is 200°C or lower, the disadvantage of shrinkage of the base material or release material of the adhesive sheet can be suppressed.

In addition, the lower the drying temperature, the greater the height difference of the formed recesses, and there is a tendency for the number of formed recesses to decrease.

In addition, a void portion (Z) is easily formed around the particle portion (Y) of the resin layer formed by this step.

By using one or more selected from the group consisting of silica particles, metal oxide particles, and bentonite as the fine particles contained in the composition (y), the void portion (Z) can be easily formed.

In addition, a layer (Xβ) that mainly contains a resin portion (X) and a particle portion formed in accordance with the adhesive sheet 1a of FIG. 1(a), etc., is produced (Y) When the layer (Y1) of 15% by mass or more and the layer (Xα) mainly containing the resin part (X) are laminated in this order, the adhesive sheet of the resin layer is preferably as follows The first and second aspect of the manufacturing method.

In addition, in the description of the manufacturing method of the first and second aspects below, "composition (xβ)" and "composition (xα)" are the same as the above-mentioned composition (x) unless otherwise specified. (xβ) or (xα) the details of each component (resin, cross-linking agent, adhesive imparting agent, general additives, dilution solvent, etc.) (specific examples of each component, preferred components, component content, solid content concentration) Etc.) is also the same as the above composition (x), and the "composition (y)" is also the same as above.

[Manufacturing method of the first aspect]

As the first aspect of the manufacturing method, it has at least the following steps (1A) and (2A): Step (1A): The base material or the release material is composed of resin and the content of fine particles is less than 15% by mass. The coating film (xβ') composed of the substance (xβ), the coating film (y') composed of the composition (y) containing 15% by mass or more of the aforementioned fine particles, and the coating film (y') composed of the resin containing less than 15 mass% of the fine particles % Of the composition (xα) of the coating film (xα') formed in the order of lamination; step (2A): at the same time the coating film (xβ') formed in step (1A), the coating film ( y') and the coating film (xα') are dried.

In step (1A), it is preferable to mix the above-mentioned solvent in composition (xβ), composition (y) and composition (xα) to form a solution form of the composition After coating.

The method of forming the coating film (xβ'), coating film (y') and coating film (xα') can be to form the coating film (xβ') on the substrate or release material, and then apply the coating film (xβ') The method of forming a coating film (y') on the coating film (y'), and then forming a coating film (xα') on the coating film (y'), is the method of successively forming using the above-mentioned coater, or the method of simultaneous coating using the above-mentioned multi-layer coater The method of forming coating film (xβ'), coating film (y') and coating film (xα') by cloth.

In addition, in this step (1A), after forming more than one layer of coating film (xβ'), coating film (y'), and coating film (xα'), proceed to step (2A) before applying Pre-drying treatment to the extent that the coating film does not undergo a hardening reaction.

For example, after forming any one of the coating film (xβ'), coating film (y'), and coating film (xα'), the above-mentioned pre-drying step may be performed each time, and the coating film (xβ') and coating film may also be formed. After the film (y'), the above-mentioned pre-drying step is performed together to form a coating film (xα').

In this step (1A), the drying temperature during the pre-drying treatment is usually set appropriately within a temperature range that does not harden the formed coating film, but preferably does not reach the drying temperature in step (2A). The specific drying temperature specified as the "drying temperature not reached in step (2A)" is preferably 10 to 45°C, more preferably 10 to 34°C, and more preferably 15 to 30°C.

Step (2A) is a step in which the coating film (xβ'), coating film (y') and coating film (xα') formed in step (1A) are dried at the same time. The preferable range of the drying temperature in this step is the same as the above Step (2) is the same. Through this step, a resin layer including a resin part (X) and a particle part (Y) is formed.

[Manufacturing method of the second aspect]

As the second aspect of the manufacturing method, at least the following steps (1B) and Step (2B): Step (1B): On the layer (Xβ) mainly containing the resin part (X) provided on the base material or the release material, according to the aforementioned composition (y) containing 15% by mass or more of fine particles The coating film (y') of the composition and the coating film (xα') composed of the composition (xα) containing the resin as the main component are sequentially laminated to form a step; Step (2B): Simultaneously use the steps (1B) The step of drying the formed coating film (y') and coating film (xα').

In the step (1B), the "layer (Xβ) mainly containing the resin part (X)" can be formed by drying the coating film (xβ') formed of the composition (xβ) containing the resin as the main component.

In order to form the layer (Xβ) from the composition (xβ), in addition to the resin, the layer (Xβ) may contain a crosslinking agent, general-purpose additives, and the like. The content of the resin part (X) in the layer (Xβ) is as described above.

As a method of forming the layer (Xβ), a coating film (xβ') made of a composition (xβ) containing resin as the main component can be formed on a substrate or release material, and the coating film (xβ') can be dried to form.

The drying temperature at this time is not particularly limited, and is preferably 35 to 200°C, more preferably 60 to 180°C, still more preferably 70 to 160°C, still more preferably 80 to 140°C.

In addition, in this aspect, it is not on the coating film (xβ'), but on the layer (Xβ) obtained after drying in order to form the coating film (y') and the coating film (xα'), and The first aspect described above is different.

In step (1B), it is also better to blend in composition (y) and composition (xα) The above-mentioned solvent is applied in the form of a solution of the composition.

The coating film (y') and coating film (xα') can be formed by forming a coating film (y') on the layer (Xβ), and then forming a coating film (xα') on the coating film (y') The method may be a method of successively forming using the above-mentioned coater, or a method of simultaneously coating and forming a coating film (y') and a coating film (xα') using the above-mentioned multi-layer coater.

In addition, in this step (1B), after the coating film (y') is formed, or after the coating film (y') and the coating film (xα') are formed, before the step (2B), the Pre-drying treatment to the extent that the coating film undergoes hardening reaction.

In this step (1B), the drying temperature during the pre-drying treatment is usually set appropriately within a temperature range that does not harden the formed coating film, but preferably does not reach the drying temperature in step (2B). The specific drying temperature specified as the "drying temperature of the step (2B) not reached" is preferably 10 to 45°C, more preferably 10 to 34°C, and still more preferably 15 to 30°C.

Step (2B) is a step in which the coating film (y') and the coating film (xα') formed in step (1B) are dried at the same time. The preferable range of the drying temperature in this step is the same as that in step (2) above. Through this step, a resin layer including a resin part (X) and a particle part (Y) is formed.

[Example]

The present invention is described in more detail with the following examples, but the present invention is not limited to the following examples. In addition, the physical property values in the following manufacturing examples and examples are the values measured by the following methods.

<Mass average molecular weight (Mw)>

Using a gel permeation chromatography device (manufactured by TOSOH Co., Ltd., product name "HLC-8020"), it was measured under the following conditions, and the value measured in terms of standard polystyrene was used.

(Measurement conditions)

‧Column: Connect "TSK protection column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL", "TSK gel G1000HXL" (all manufactured by TOSOH Co., Ltd.) in order

‧Column temperature: 40℃

‧Developing solvent: tetrahydrofuran

‧Flow rate: 1.0mL/min

<Measurement of Volume Average Secondary Particle Size of Silica Particles>

The volume average secondary particle size of the silica particles is obtained by measuring the particle size distribution by the Coulter counting method using a Multisizer 3 machine or the like (manufactured by Beckman Coulter).

<Measurement of the thickness of the resin layer>

Use the constant pressure thickness tester (model: "PG-02J", standard specification: according to JIS K6783, Z1702, Z1709) manufactured by TECLOCK Co., Ltd. for measurement.

Specifically, after measuring the total thickness of the adhesive sheet to be measured, the value obtained by subtracting the thickness of the substrate or the peeling sheet measured in advance is set as the "thickness of the resin layer".

Manufacturing example x-1~x-4 (Preparation of resin composition solution (xβ-1)~(xβ-2) and (xα-1)~(xα-2))

To the acrylic resin solution of the adhesive resin of the type and solid content described in Table 1, the crosslinking agent and the adhesive imparting agent of the type and blending amount described in Table 1 were added. Next, use the dilution solvents listed in Table 1 to prepare solutions (xβ-1)~(xβ-2) and (xα-1)~(xα-2) of the resin composition with the solid content concentration listed in Table 1. .

In addition, the details of the components described in Table 1 used in the preparation of the solutions (xβ-1) to (xβ-2) and (xα-1) to (xα-2) of the resin composition are as follows.

<Solution of Acrylic Resin>

‧Solution (i): solid containing acrylic resin (xi) (acrylic copolymer with constituent units derived from raw monomers formed by BA/AA=90/10 (mass%), Mw: 630,000) A mixed solution of toluene and ethyl acetate with a component concentration of 34.0% by mass.

‧Solution (ii): Containing acrylic resin (x-ii) (Acrylic copolymer with constituent units derived from raw monomers formed by BA/AA=90/10 (mass%), Mw: 470,000) A mixed solution of toluene and ethyl acetate with a solid content concentration of 37.0% by mass.

‧Solution (iii): Acrylic copolymer containing acrylic resin (x-iii) (sourced from 2EHA/VAc/AA=75/23/2 (mass%) as the constituent unit of the raw material monomer, Mw : 660,000) a mixed solution of toluene and isopropyl alcohol (IPA) with a solid content concentration of 37.0% by mass.

‧Solution (iv): Acrylic copolymer containing acrylic resin (x-iv) (with the constituent units of raw monomers derived from BA/AA/HEA=94/3/3 (mass%), Mw : 1 million) ethyl acetate solution with a solid content concentration of 37.0% by mass.

In addition, the abbreviations of the constituent raw material monomers of the above-mentioned acrylic copolymer are as follows.

‧BA: n-Butyl Acrylate

‧2EHA: 2-ethylhexyl acrylate

‧AA: Acrylic

‧VAc: Vinyl Acetate

‧HEA: 2-hydroxyethyl acrylate

<Crosslinking agent>

‧Al-based cross-linking agent: product name "M-5A", manufactured by Soken Chemical Co., Ltd., aluminum chelate-based cross-linking agent, solid content = 4.95 mass%.

‧Epoxy crosslinking agent: "TETRAD-C" (product name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is diluted with toluene to make a solution of epoxy crosslinking agent with a solid content of 5 mass%.

<Adhesive imparting agent>

‧Turpentine ester series TF: Rosin ester series polymer, Mw: less than 10,000, softening point: 85℃

‧Styrene-based TF: a combination of styrene-based monomers and aliphatic-based monomers Polymer, Mw: less than 10,000, softening point: 95℃

<Dilution solvent>

‧Mixed solvent (1): Toluene/isopropanol (IPA) = 65/35 (mass ratio) mixed solvent.

‧Mixed solvent (2): A mixed solvent of ethyl acetate/IPA=86/14 (mass ratio).

Manufacturing example f-1 (Preparation of fine particle dispersion (f-1))

Compared to the solution (i) containing the acrylic resin containing the above acrylic resin (xi) (acrylic copolymer having constituent units derived from butyl acrylate (BA) and acrylic acid (AA), BA/AA=90/ 10 (mass %), Mw: 630,000) 100 parts by mass of a mixed solution of toluene and ethyl acetate with a solid content of 34.0% by mass (solid content: 34.0% by mass), adding silica particles as fine particles (product name) "NIPSIL E-200A", manufactured by TOSOH SILICA, volume average secondary particle size: 3μm) 51.0 parts by mass (solid content: 51.0 parts by mass) and toluene to disperse fine particles to prepare a preparation containing acrylic resin and silica particles A fine particle dispersion liquid (f-1) with a solid content concentration of 27% by mass.

Manufacturing example f-2 (Preparation of fine particle dispersion (f-2))

Instead of solution (i), with respect to solution (ii) containing the above-mentioned acrylic resin (x-ii) (acrylic copolymer having structural units derived from butyl acrylate (BA) and acrylic acid (AA), BA/ AA=90/10 (mass%), Mw: 470,000) 100 parts by mass of a mixed solution of toluene and ethyl acetate with a solid content concentration of 37.0% by mass (solid content: 37.0% by mass), adding silica as fine particles Particles (product name "NIPSIL E-200A", manufactured by TOSOH SILICA, volume average secondary particle size: 3μm) 55.5 parts by mass (solid content: 55.5 parts by mass) and toluene to disperse the fine particles to prepare There is a fine particle dispersion liquid (f-2) with a solid content of 30% by mass of acrylic resin and silica particles.

Manufacturing example y-1~y-2 (Preparation of coating liquid (y-1)~(y-2) for coating film (y’) formation)

Add the type and amount of fine particle dispersion, acrylic resin solution, crosslinking agent, and diluting solvent listed in Table 2 to prepare the coating solution for coating film (y') formation with the solid content concentration listed in Table 2. (y-1)~(y-2).

In addition, the details of each component described in Table 2 used in the preparation of the coating liquids (y-1) to (y-2) for forming the coating film (y') are as follows.

<Fine Particle Dispersion Liquid>

‧Dispersion (f-1): The fine particle dispersion (f-1) containing acrylic resin (x-i) and silica particles with a solid content concentration of 27% by mass prepared in Production Example f-1.

‧Dispersion (f-2): The fine particle dispersion (f-2) containing acrylic resin (x-ii) and silica particles with a solid content concentration of 30% by mass prepared in Production Example f-2.

<Solution of Acrylic Resin>

‧Solution (i): solid containing acrylic resin (xi) (acrylic copolymer with constituent units derived from raw monomers formed by BA/AA=90/10 (mass%), Mw: 630,000) Nail with a component concentration of 34.0% by mass A mixed solution of benzene and ethyl acetate.

‧Solution (ii): Containing acrylic resin (x-ii) (Acrylic copolymer with constituent units derived from raw monomers formed by BA/AA=90/10 (mass%), Mw: 470,000) A mixed solution of toluene and ethyl acetate with a solid content concentration of 37.0% by mass.

<Crosslinking agent>

‧Al-based cross-linking agent: product name "M-5A", manufactured by Soken Chemical Co., Ltd., aluminum chelate-based cross-linking agent, solid content = 4.95 mass%.

‧Epoxy crosslinking agent: "TETRAD-C" (product name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is diluted with toluene to make a solution of epoxy crosslinking agent with a solid content of 5 mass%.

<Dilution solvent>

‧IPA/CHN: A mixed solvent composed of isopropyl alcohol (IPA) and cyclohexanone (CHN) (IPA/CHN=95/5 (mass ratio)).

Examples 1~2 (1) Formation of coating film

On the release agent layer of the release film of the first release material (manufactured by LINTEC Co., Ltd., product name "SP-PET381031", thickness 38μm, with a silicone release agent layer on one side of the PET film), Using a multi-layer die nozzle coater (width: 250mm) from the release agent layer, the resin composition solution (xβ-1) prepared in the production example x-1 described in Table 3 and the production example y- were applied at the same time 1 The prepared coating liquid (y-1) for forming the coating film (y') and the production example for the formation of the coating film (xα') x-1 The prepared resin composition solution (xβ-1), according to the coating The film (xβ'), the coating film (y'), and the coating film (xα') are formed simultaneously in this order.

In addition, the coating speed of each solution (coating liquid) used to form the coating film (xβ'), coating film (y') and coating film (xα') and the coating amount of each coating film are shown in Table 3. Record.

(2) Drying treatment

Then, the three layers of coating film (xβ'), coating film (y') and coating film (xα') are dried simultaneously at a drying temperature of 100°C for 2 minutes to form a resin part (X) and a particle part (Y) The thickness of the resin layer shown in Table 3.

In addition, in any of Examples 1 to 2, the surface (α) of the formed resin layer was visually confirmed with a plurality of recesses and flat surfaces.

(3) Production of adhesive sheets without substrates and adhesive sheets with substrates

On the surface (α) of the formed resin layer, the peeling from the second peeling material is thin The release agent layer of the film (manufactured by LINTEC Co., Ltd., product name "SP-PET386040") is laminated on the surface to produce a substrate-free adhesive sheet.

And after the above-mentioned non-substrate adhesive sheet produced in the same manner was allowed to stand at 23°C for 1 week, the first release material was removed to expose the surface (β) of the resin layer and the polyethylene terephthalate of the substrate (PET) film (manufactured by TORAY Co., Ltd., product name "LUMIRROR T60 #50", thickness 50μm) is laminated by laminating to produce an adhesive sheet with a substrate.

Examples 3~4 (1) Formation of coating film

Coating on the surface of the aluminum vapor deposition layer of a polyethylene terephthalate (PET) film (made by LINTEC Co., Ltd., "FNS keshi N50", thickness 50μm) with an aluminum vapor deposition layer on one side, using a multilayer die The device (width: 250mm) starts from the aluminum vapor-deposited layer and is simultaneously coated with the resin composition solution (xβ-2) prepared in Manufacturing Example x-2 and the coating prepared in Manufacturing Example y-2 as described in Table 3 at the same time. The coating solution (y-2) for forming the film (y') and the resin composition solution (xα-1) or (xα-2) prepared by the production examples x-3 to x-4, depending on the coating film (xβ' ), the coating film (y') and the coating film (xα') are formed at the same time.

In addition, the coating speed of each solution (coating liquid) used to form the coating film (xβ'), coating film (y') and coating film (xα') and the coating amount of each coating film are shown in Table 3. Record.

(2) Drying treatment

Then, the three layers of coating film (xβ'), coating film (y') and coating film (xα') are dried simultaneously at a drying temperature of 100°C for 2 minutes to form a resin part (X) and a particle part (Y) The thickness of the resin layer shown in Table 3.

In addition, in any of Examples 3 to 4, a plurality of recesses and flat surfaces were visually confirmed on the surface (α) of the formed resin layer.

(3) Production of adhesive sheet with substrate

It was laminated to the surface of the release agent layer of a release film (manufactured by LINTEC Co., Ltd., product name "SP-PET 381031") to produce an adhesive sheet with a substrate.

Comparative example 1~4 (1) Production of embossed release paper

A 25μm thick resin film made of low-density polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., product name "SUMIKATHENE (L705)", melting point 106°) is formed on one side of the fine paper. Then, on the resin film The surface is closely adhered to the uneven surface of the metal engraving plate. In this state, it is inserted between two rotating silicone rubber rolls heated at 115°C to emboss the surface of the resin film.

Coat the surface of the embossed resin film with a silicone-based release agent (manufactured by LINTEC, product name "the same release agent as SP-PET1031"), and then dry it at 100°C for 1 minute to produce a press with a thickness of 110 μm Textured release paper.

In addition, the concave-convex forming surface of the metal engraving plate is processed by using the method of forming the concave portion and the flat surface of the individual shape on the resin layer surface (α) of the adhesive sheet produced in Comparative Examples 1 to 4.

(2) Production of adhesive sheet with base material

On the release agent layer of the embossed release paper produced in (1) above, use an applicator to coat the solution (xβ-1) of the resin composition prepared in Production Example x-1 described in Table 1, and then apply 100 After drying at °C for 1 minute, the resin layer was formed so that the coating speed and the coating amount of each coating film described in Example 1 of Table 3 were obtained.

Next, a PET film (manufactured by Toray Co., Ltd., product name "LUMIRROR T60 #50", thickness 50 μm) was laminated on the surface (α) of the resin layer to produce an adhesive sheet with a substrate.

Using the base-free adhesive sheet or the base-attached adhesive sheet produced in the Examples and Comparative Examples, the resin layer of the adhesive sheet and the characteristics of the adhesive sheet were measured or observed by the following methods. The results are shown in Table 4 and Table 5.

(1) Production of measurement samples

As shown in Figure 6(a), in order to eliminate the influence of the undulation of the adhesive sheet, the non-alkali glass (product name "EAGLE XG", Corning Incorporated) of the adherend 101 with a smooth surface is attached through double-sided tape. The base material of the adhesive sheet made in the embodiment and the comparative example.

Next, the release material laminated on the surface (α) of the resin layer of the adhesive sheet is removed, and the surface (α) of the resin layer is exposed as a measurement sample.

(2) Image acquisition of area (D) and area (Q) on the surface (α)

Use a digital microscope (50 times magnification) to examine the exposed resin layer surface (α) of the above-mentioned measurement sample, and select a range of adjoining multiple images on the photographing surface (α) in the A direction of Fig. 6(a). Use the image link function of the digital microscope to obtain the linked link image.

In addition, during this shooting, more specifically, the focus is sequentially moved from the direction of A in FIG. 6(a) from above the part judged to be a flat surface by visual observation, and the part that has the focus initially is taken as the flat surface.

Next, in the obtained connected image, select a region (D) surrounded by a rectangle with a length of 8 mm × a width of 10 mm arbitrarily, and set it as the "image of region (D)".

In addition, among the obtained connected images, an area (Q) surrounded by a square of 1 mm on one side of one area is arbitrarily selected, and this is set as the "image of area (Q)".

In addition, the imaging conditions of the digital microscope in (2) above are as follows.

(Measuring equipment)

Manufactured by KYENCE Co., Ltd., product name "Digital Microscope VHX-5000", high-resolution zoom lens VHX-ZST100 times

(Measurement conditions)

‧Epi-illumination: turn on

‧Platform through lighting: off

‧Lighting conversion: coaxial epi-shooting

‧Edge emphasis: off

(3) Measurement of the area of the concave part and the flat surface and the circumference of the flat surface in the area (D)

Based on the "image of the area (D)" obtained in (2) above, use the same digital microscope as the above to perform automatic area measurement to obtain the areas of the recesses and flat surfaces in the area (D) respectively.

In addition, the automatic area measurement is to measure the numerical value (area) of the resulting binary image after digital microscope and visual image processing and binarization of the flat surfaces and recesses that exist in the area (D) , Respectively measure the area of each recess and each flat surface. When there is a plural number of recesses and flat surfaces, respectively, the area measurement of the recesses and the flat surface is performed.

The automatic area measurement conditions are as follows.

(Automatic area measurement conditions)

‧Extract mode: Brightness (weak noise removal)

‧Extract area: Specify a value (rectangular) to extract a rectangle with a length of 8mm × a width of 10mm

‧Shaping the extraction area: remove particles (removal area less than ^{100μm 2)}

Moreover, by the same automatic measurement, the circumference of each flat surface in the area (D) is also measured.

In addition, when it is impossible to determine whether it is a flat surface by visual inspection of the image, the light-transmitting smooth surface is adhered to the surface of the resin layer (α) by hand using a squeegee without applying load as much as possible. The W direction of Fig. 6(b), the interface between the smooth surface 100a of the light-transmitting adherend 100 and the surface (α) 12a of the resin layer 12 is photographed. It is judged that the surface (α) 12a is attached to the smooth surface 100a Part has a flat surface.

In addition, the light-transmitting adherend 100 having a smooth surface 100a, like the "adherent having a smooth surface", uses alkali-free glass (product name "EAGLE XG", manufactured by Corning Incorporated).

The data obtained from the area of each recess and the area of the flat surface and the surrounding length are sorted using chart software (Japan Microsoft Corporation, EXCEL).

Then, from this data, extract the data of the "flat surface (S)" obtained by removing the flat surface with a cumulative relative frequency of 30% or less from the smaller area of each flat surface and the relative frequency. Furthermore, the average value of the peripheral length of the flat surface (S) and the average value of the area of the flat surface (S) are calculated.

Furthermore, calculate the standard deviation of the peripheral length or area of the flat surface (S) relative to the average value when the total length or area of the flat surface (S) is set to 100 The skewness Sk value and kurtosis Ku value of the normal distribution curve of the difference and flat surface (S) relative to the surrounding length or area and frequency. The calculated results are shown in Table 4.

In addition, the skewness Sk value is based on the following formula (1), and the kurtosis Ku value is based on the following formula (2), and is calculated using graph software (Microsoft Corporation, Japan, EXCEL).

[In formula (1), n represents the number of flat surfaces (S), x _i represents the surrounding length or area of each flat surface (S) (i: 1, 2,...n), μ represents each flat surface (S) is the average of the surrounding length or area, s represents the standard deviation of the specimen].

[In formula (2), n represents the number of flat surfaces (S), x _i represents the surrounding length or area of each flat surface (S) (i: 1, 2,...n), μ represents each flat surface (S) is the average of the surrounding length or area, s represents the standard deviation of the specimen].

Below, the evaluation criteria for the items listed in Table 5 are displayed.

<Is it possible to visually confirm the concave part and flat surface>

‧Evaluation item (a): Visually observe the measurement made in (1) above The exposed resin layer surface (α) of the sample was evaluated by the following criteria to determine whether the recesses and flat surfaces on the surface (α) can be visually confirmed.

A: The existence of recesses and flat surfaces on the surface (α) can be confirmed visually.

F: The existence of recesses and flat surfaces on the surface (α) cannot be visually confirmed.

<About the evaluation of the shape of the concave part and the flat surface>

Observe the following evaluation items (b1)~(b4) and (c1)~(c4) from the "image of area (D)" or "image of area (Q)" obtained from (2) above, Evaluation is based on individual benchmarks.

(Evaluation items for the shape and position of the flat surface in the area (D))

‧Evaluation item (b1): From the acquired "image of area (D)", use the following criteria to evaluate whether there is an amorphous flat surface in the area (D).

A: There are plural amorphous flat surfaces.

B: There is only one amorphous flat surface.

C: An amorphous flat surface is partially present.

‧Evaluation item (b2): From the acquired "image of area (D)", use the following criteria to evaluate whether the area (D) has a width that can select the area surrounded by a circle with a diameter of 100μm or more Flat surface.

A+: In the region (D), there is a flat surface having a width that can select a region surrounded by a circle with a diameter of 200 μm.

A: In the region (D), there is a flat surface having a width that can be selected from the region surrounded by a circle with a diameter of 150 μm.

B: In the region (D), there is a flat surface having a width that can select a region surrounded by a circle with a diameter of 100 μm.

C: In the region (D), there is no flat surface having a width that can select the region surrounded by a circle with a diameter of 100 μm.

‧Evaluation item (b3): From the acquired "image of area (D)", use the following criteria to evaluate whether the location of multiple flat surfaces in the area (D) has periodicity.

A: The position where the complex flat surface exists does not have periodicity

F: The location where the complex flat surface exists is periodic, or there is no complex flat surface in the region (D).

‧Evaluation item (b4): From the acquired "image of area (D)", use the following criteria to evaluate whether the flat surface shape existing in the area (D) has a shape that becomes a fixed repeating unit.

A: The flat surface shape does not have a shape that becomes a fixed repeating unit.

F: The flat surface shape has a shape that becomes a fixed repeating unit.

(Evaluation items on the shape and position of the recesses in the area (D))

‧Evaluation item (c1): From the acquired "image of area (D)", use the following criteria to evaluate whether there is an amorphous recess in the area (D).

A: There are amorphous recesses in the plural.

B: There is only one amorphous recess.

C: There are no amorphous recesses.

‧Evaluation item (c2): From the acquired "image of area (D)", use the following criteria to evaluate whether there are multiple recesses in the area (D) and whether the locations where the multiple recesses exist are periodic.

A: The position where the plural recesses exist does not have periodicity

F: The position where the plural recesses exist is periodic, or the plural recesses do not exist in the area (D).

‧Evaluation item (c3): From the acquired "image of area (D)", use the following criteria to evaluate whether the shape of the recesses in the area (D) has a shape that becomes a fixed repeating unit.

A: The shape of the recess does not have a shape that becomes a fixed repeating unit.

F: The shape of the recess has a shape that becomes a fixed repeating unit.

(Evaluation items for the presence or absence of amorphous recesses in the area (Q))

‧Evaluation item (c4): From the acquired "image of area (Q)", use the following criteria to evaluate whether there is an amorphous recess in the area (Q).

A: In the region (Q), there are a plurality of amorphous recesses.

B: In the region (Q), there is only one amorphous recess.

C: In the region (Q), there are no amorphous recesses.

<Proportion of area occupied by flat surface or recess>

Based on the removal of the area (D) before the area (D) of all flat surfaces and recesses that exist in the area (D) before the "accumulative relative frequency of 30% or less of the flat surface obtained by adding the relative frequency from the smaller area of each flat surface) obtained from the above (3) Area data, calculate the "area ratio (%) of flat surface" to the total area of the area (D) And "Proportion of area occupied by recesses (%)".

Using this data, the calculation or evaluation of the physical property values of the following evaluation items (d1) to (d2) and (e1) to (e2) are also performed.

<Evaluation of the area of the flat surface and the concave part in the region (D)>

‧Evaluation item (d1): Use the following criteria to evaluate whether there is a ^{flat surface with an area of 0.2mm 2} or more in the area (D).

A+: There are plural ^{flat surfaces with an area of 0.4 mm 2} or more.

A: There is one flat surface with an area of 0.4 mm ² or more, and there are a plurality of flat surfaces with an area of 0.2 mm ² or more and less than 0.4 mm ² .

B+: There are plural flat surfaces ^{with an area of 0.2 mm 2} or more and less than 0.4 mm ^2.

B: There is one flat surface with an area of 0.2 mm ² or more and less than 0.4 mm ^2.

C: The maximum area of the flat surface existing in the region (D) is less than 0.2 mm ² .

‧Evaluation item (d2): Calculate the area ratio of the amorphous flat surface in the area (D) to the total area of the flat surface in the area (D), and evaluate it based on the following criteria.

A+: The proportion of the area occupied by the amorphous flat surface is 100%.

A: The proportion of the area occupied by the amorphous flat surface is more than 90% and less than 100%.

B: The proportion of the area occupied by the amorphous flat surface is more than 80% and less than 90%.

C: The proportion of the area occupied by the amorphous flat surface is less than 80%.

‧Evaluation item (e1): Calculate the area ratio of the recesses with the largest area in the region (D) to the total area of the recesses in the region (D) from the following formula.

[The proportion of the area occupied by the recess with the largest area (%)]=[The recess with the largest area]/[Total area of the recess]×100

‧Evaluation item (e2): Calculate the proportion of the area occupied by the amorphous recesses in the region (D) for the total area of the recesses in the region (D), and evaluate it based on the following criteria.

A+: The proportion of the area occupied by the amorphous concave portion is 100%.

A: The proportion of the area occupied by the amorphous concave portion is 90% or more and less than 100%.

B: The proportion of the area occupied by the amorphous concave portion is 80% or more and less than 90%.

C: The proportion of the area occupied by the amorphous concave portion is less than 80%.

<About the evaluation of the profile of the area (P)>

As shown in FIG. 4, an area (P) surrounded by a square 50 with a side of 5 mm on the surface (α) 12a of the resin layer 12 of the resin layer 12 with the base-material-attached adhesive sheet for removing the release material produced in the examples and comparative examples is arbitrarily selected.

Next, as shown in Figure 4, using a scanning electron microscope (manufactured by Hitachi, Ltd., product name "S-4700"), observe the square 50 passing through the area (P) under the conditions of an acceleration voltage of 5kV and a magnification of 500 times. 2 diagonal lines 51, 52, and relative to the area on the surface (α) 12a (P) Cut the two cross-sections 61 and 62 of the adhesive sheet in the thickness direction on a vertical plane to obtain two cross-sectional images.

Using these two cross-sectional images, the following evaluation items (f), (g1) to (g2), and (h1) to (h3) were evaluated.

‧Evaluation item (f): On the surface (α) side of the two cross-sectional images obtained, use the following criteria to evaluate whether there are multiple recesses specified by the following requirement (I) and flat portions specified by the following requirement (II) .

‧Requirement (I): On the surface (α) 12a side of the obtained cross-sectional image, there is a maximum height difference of more than 40% of the total thickness of the resin layer 12, and the shape of the cut part is different from each other in plural Recess.

‧Requirement (II): On the side of the surface (α) 12a of the acquired cross-sectional image, there is a cut portion corresponding to the flat surface existing in the area (P), and is connected to the resin layer 12 of the substrate 11 The contact surface is a slightly parallel flat part.

(Evaluation criteria)

A: Either one of the two acquired cross-sectional images satisfies requirements (I) and (II) at the same time.

B: Only one of the two acquired cross-sectional images satisfies requirements (I) and (II) at the same time.

C: Among the two acquired cross-sectional images, no cross-sectional images satisfying requirements (I) and (II) at the same time have been confirmed.

Also, for the adhesive sheet evaluated as "A" or "C" in the above evaluation item (f), select one cross-sectional view from the two cross-sectional images Like, perform the following evaluation items (g) and (h1)~(h3).

On the other hand, for the adhesive sheet evaluated as "B" in the above evaluation item (f), the following evaluation was performed using a cross-sectional image that satisfies both requirements (I) and (II).

(Requirements for the recesses on the side of the cross-sectional surface (α))

‧Evaluation item (g1): As shown in Figure 5, in the cross-sectional image obtained, calculate the horizontal width (E _α ) of the resin layer 12 relative to the surface (α) 12a side of 100, and the surface (α) 12a The ratio of the total width of the aforementioned recesses 13a that exists.

‧Evaluation item (g2): In the obtained cross-sectional image, evaluate whether there is a maximum height difference of 0.5 μm or more on the surface (α) 12a side according to the following criteria.

A: There are recesses with a maximum height difference of 0.5 μm or more.

F: There is no concave portion having a maximum height difference of 0.5 μm or more.

(Requirements for the flat part that exists on the side of the section surface (α))

‧Evaluation item (h1): As shown in Figure 5, in the cross-sectional image obtained, calculate the horizontal width (E _α ) of the resin layer 12 relative to the surface (α) 12a side of 100, and the surface (α) 12a The proportion of the aforementioned flat portion 14a that exists.

‧Evaluation item (h2): In the obtained cross-sectional image, evaluate whether there are multiple flat portions 14a on the surface (α) 12a side and whether the positions where the multiple flat portions 14a exist are periodic based on the following criteria.

A: There are plural flat parts, and the position where the plural flat parts exist does not have periodicity.

B: There are plural flat parts, but the positions where the plural flat parts exist are periodic.

C: There is no plural flat surface.

‧Evaluation item (h3): In the obtained cross-sectional image, evaluate whether there are multiple flat portions 14a on the surface (α) 12a side, and whether the distance between each of the multiple flat portions 14a and the substrate 11 is slightly the same.

A: There are plural flat parts, and the distance from each of the plural flat parts to the substrate is slightly the same.

B: There are a plurality of flat portions, but the distances from each of the plurality of flat portions to the base material are different from each other.

C: There is no plural flat surface.

<Quality retention rate of the resin layer of the adhesive sheet>

After obtaining the monomer of the resin layer from the adhesive sheet, measure the quality of the resin layer before heating. Next, this resin layer was poured into a muffler (manufactured by Denken Co., Ltd., product name "KDF-P90"), and heated at 800°C for 30 minutes. Next, the mass of the resin layer after heating was measured, and the mass retention rate of the resin layer was calculated by the following formula. The values are shown in Table 5.

Resin layer mass retention rate (%)=[resin layer mass after heating]/[resin layer mass before heating]×100

<Degassing>

The adhesive sheet with the base material set to the size of 50mm in length × 50mm in width is attached to the melamine-coated board of the adherend to generate air accumulation, and the surrounding area of the air accumulation is strongly pressed with a scraper. Those who hold the 2 of the time weakly. Next, when using a squeegee to remove air traps, the presence of air traps after sticking was observed, and the degassing properties of each adhesive sheet were evaluated based on the following criteria. The evaluation results are shown in Table 5.

5: In either of the weaker pressing and the stronger pressing, the air accumulation disappears.

4: When the pressure is weak, the air accumulation disappears. When it is pressed strongly, most of the air accumulation disappears, and the remaining air accumulation disappears if it is pressed again.

3: When the pressure is weak, the air accumulation disappears. On the other hand, when the pressure is strong, there are parts where some air remains.

2: When weakly pressed, most of the air accumulation disappears, and the remaining air accumulation disappears if it is pressed again. On the other hand, when pressed strongly, residual air will accumulate.

1: In either of the weak pressing and the strong pressing, the air accumulation remains.

<Adhesion>

After cutting the adhesive sheet with base material produced in the examples and comparative examples to a size of 25mm in length×300mm in width, under an environment of 23°C and 50%RH (relative humidity), the surface of the resin layer of the adhesive sheet (α) Attach it to a stainless steel plate (SUS304, No. 360 grinding), and let it stand for 24 hours in the same environment. After standing, the adhesive force of each adhesive sheet was measured by the 180° peeling method at a stretching speed of 300 mm/min based on JIS Z0237: 2000. The measurement results are shown in Table 5.

<Burst resistance>

The adhesive sheet with a base material of 50mm in length × 50mm in width is attached to a polymethyl methacrylate board of 70mm in length × 150mm in width × 2mm in thickness (manufactured by Mitsubishi Acrylic, product name "ACRYLITE L001") , Use a scraper to press strongly to make test samples.

After the test sample was allowed to stand at 23°C for 12 hours, it was allowed to stand in a hot air dryer at 80°C for 1.5 hours, and then placed in a hot air dryer at 90°C for 1.5 hours, and the bursting state after heating promotion was visually observed. , Use the following criteria to evaluate the burst resistance of each adhesive sheet. The evaluation results are shown in Table 5.

A: No burst was confirmed at all.

B: A burst is partially confirmed.

C: A burst is fully confirmed.

The adhesive sheets of Examples 1 to 4 have a resin layer with recesses and a flat surface on the adhesive surface, and the long distribution around the flat surface or the area distribution of the flat surface falls within a specific range, so it has excellent outgassing The performance and adhesion characteristics can be well-balanced to show the results.

On the other hand, the pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 were inferior to the pressure-sensitive adhesive sheets of Examples.

Fig. 7(a) and Figs. 8 to 14 are the free selection of the exposed surface (α) of the resin layer of the adhesive sheet produced in Examples 1 to 4 and Comparative Examples 1 to 4, respectively, taken from the surface (α) side using a digital microscope By length 8mm×width 10mm The binarized image of the image obtained from the area (D) enclosed by the rectangle.

That is, the rectangular image in Fig. 7(a) and Figs. 8 to 14 has a length of "8mm" and a width of "10mm".

In addition, in these binary images, the black part is a flat surface, and the white part corresponds to a concave part.

Fig. 7(b) is a cross-sectional image obtained by observing the cross-section of the adhesive sheet made in Example 1 using a scanning microscope. In addition, the cross-sections of the adhesive sheets of Examples 2 to 4 are also similar to the cross-sectional images of FIG. 5.

[Industrial availability]

The adhesive sheet in the same state of the present invention can be used for identification or decoration, coating masking, surface protection of metal plates, etc., and can be used as an adhesive sheet with a large attachment area.

1a, 1b, 2a, 2b‧‧‧ adhesive sheet

11‧‧‧Substrate

12‧‧‧Resin layer

12a‧‧‧surface (α)

12b‧‧‧Surface (β)

(X)‧‧‧Resin part (X)

(Y)‧‧‧Particle part (Y)

(Xβ)‧‧‧Layer (Xβ) mainly containing resin part (X)

(Xα)‧‧‧Layer (Xα) mainly containing resin part (X)

(Y1)‧‧‧Layer (Y1) containing 15% by mass or more of particles (Y)

13‧‧‧Concave

14‧‧‧Flat surface

21‧‧‧Striping material

22‧‧‧Striping material

Claims (28)

An adhesive sheet, which has a resin layer on a substrate or release material, and has adhesiveness at least on the surface (α) of the resin layer opposite to the side where the substrate or release material is provided, And on the surface (α) there are recesses and a plurality of flat surfaces. On the surface (α), the arbitrarily selected area (D) surrounded by a rectangle with a length of 8 mm × a width of 10 mm, there are a plurality of flat surfaces, And the aforementioned plural flat surfaces satisfy at least one of the following requirements (1) and (2); ‧Requirement (1): remove the aforementioned plural flat surfaces from the smaller area of each flat surface and add the relative number of times If the sum of the peripheral lengths of more than one flat surface (S) is set to 100, the standard for the average value of the peripheral length relative to the flat surface (S) is a flat surface with a cumulative relative frequency of 30% or less. The deviation is 0.33 or more; ‧Requirement (2): Remove the flat surface of less than 30% of the cumulative relative frequency obtained by adding the relative frequency from the smaller area of each flat surface from the aforementioned plural flat surfaces, and obtain 1 When the total area of more than one flat surface (S) is set to 100, the standard deviation relative to the average area of the flat surface (S) is 0.39 or more. For example, the adhesive sheet of claim 1, which satisfies the aforementioned requirements (1) and (2) at the same time. For example, the adhesive sheet of claim 1 or 2, which satisfies the aforementioned requirement (1), and also satisfies the following requirements (1-1): ‧Requirement (1-1): the length of each flat surface (S) relative to the surrounding The skewness Sk value of the normal distribution curve with frequency is 1.0 or more. For example, the adhesive sheet of claim 3 satisfies the aforementioned requirement (1), and also satisfies the following requirements (1-2): ‧Requirement (1-2): the relative length and frequency of each flat surface (S) The kurtosis Ku value of the normal distribution curve is above 0.3. For example, the adhesive sheet of claim 1 or 2, which satisfies the aforementioned requirement (2), and also satisfies the following requirements (2-1): ‧Requirement (2-1): the relative area of each flat surface (S) and The skewness Sk value of the normal distribution curve of frequency is 1.0 or more. For example, the adhesive sheet of claim 5 satisfies the aforementioned requirement (2), and also satisfies the following requirements (2-2): ‧Requirement (2-2): the relative area and frequency of each flat surface (S) The kurtosis Ku value of the normal distribution curve is above 1.8. The adhesive sheet of claim 1, wherein the shape of the flat surface viewed from the surface (α) side is amorphous. Such as the adhesive sheet of claim 1, wherein the area (P) on the surface (α) surrounded by a square of 5 mm on one side is arbitrarily selected, and the area (P) that passes through the two diagonals of the square is opposite to the surface (α) The area (P) is like a vertical plane, and at least one of the two cross-sections (P1) obtained by cutting the aforementioned adhesive sheet in the thickness direction exists on the surface (α) side of the aforementioned cross-section (P1) A plurality of recesses having a maximum height difference of 40% or more of the total thickness of the resin layer, and the shape of the cut portion is different from each other, and the cut portion of the flat surface that should exist in the region (P), And the surface in contact with the aforementioned substrate or the aforementioned resin layer of the release material is slightly flat The flat part of the line. Such as the adhesive sheet of claim 8, wherein in the aforementioned section (P1), there are a plurality of flat portions on the surface (α) side. Such as the adhesive sheet of claim 9, wherein in the aforementioned section (P1), the positions of the aforementioned plural flat portions existing on the surface (α) side do not have periodicity. The adhesive sheet of claim 9 or 10, wherein in the cross-section (P1), the distances from the plurality of flat portions on the surface (α) side to the substrate or release material are the same. Such as the adhesive sheet of claim 8, wherein when the plurality of the aforementioned cross-sections (P1) are obtained, the formation position and the formation length of the flat portions existing on the surface (α) side of the respective cross-sections (P1) are obtained by The plural sections (P1) are different from each other. Such as the adhesive sheet of claim 1, wherein the aforementioned recesses have a maximum height difference of 0.5 μm or more. Such as the adhesive sheet of claim 1, wherein there are more than one flat surface (f1) on the surface (α) of the aforementioned resin layer, and the flat surface (f1) has a width that can be selected from an area surrounded by a circle with a diameter of at least 100 μm . Such as the adhesive sheet of claim 1, wherein there are more than one flat surface (f2) on the surface (α) of the aforementioned resin layer, and the flat surface (f2) has an area of ^{0.2 mm 2 or more.} Such as the adhesive sheet of claim 1, wherein the aforementioned recesses are not formed by using a peeling material with embossed patterns. Such as the adhesive sheet of claim 1, wherein the aforementioned resin layer comprises: The resin part (X) containing resin, and the particle part (Y) composed of fine particles. Such as the adhesive sheet of claim 17, wherein in the aforementioned section (P1), the particle portion (Y) contained in the aforementioned resin layer has an uneven distribution in the horizontal direction, and is relative to the surface (α) Concavity, the distribution of the particle portion (Y) in the region (s1) below the concavity in the thickness direction is at the same level as the region (s1) and the region (s2) with a flat portion on the surface (α) Less than for. The adhesive sheet of claim 17 or 18, wherein the mass retention rate after heating the aforementioned resin layer at 800°C for 30 minutes is 3 to 90% by mass. The adhesive sheet of claim 17 or 18, wherein the aforementioned resin contained in the resin portion (X) contains an adhesive resin. The adhesive sheet of claim 17 or 18, wherein the resin portion (X) further contains one or more selected from the group consisting of a metal chelate crosslinking agent and an epoxy crosslinking agent. The adhesive sheet of claim 17 or 18, wherein the aforementioned fine particles are one or more selected from the group consisting of silica particles, oxide metal particles, and bentonite. The adhesive sheet of claim 1, wherein the surface (β) of the resin layer on the side where the substrate or release material is provided has adhesiveness. The adhesive sheet of claim 1, wherein the aforementioned resin layer is from the side where the base material or the release material is provided, according to the layer (Xβ) mainly containing the resin part (X), the layer containing 15% by mass or more of the particle part (Y) (Y1), and main A multilayer structure formed by sequentially laminating layers (Xα) containing the resin portion (X). Such as the adhesive sheet of claim 24, wherein the layer (Xβ) is a layer formed of a composition (xβ) containing resin and the content of fine particles is less than 15% by mass, and the layer (Y1) is composed of a resin containing 15% by mass or more of fine particles The layer formed by the composition (y), the layer (Xα) is a layer formed by the composition (xα) containing resin and the content of fine particles is less than 15% by mass. A method for manufacturing an adhesive sheet, which is a method for manufacturing an adhesive sheet as claimed in any one of claims 1 to 24, and has at least the following steps (1) and (2); Step (1): forming a resin containing resin and The step of a coating film (x') composed of a composition (x) whose content of fine particles is less than 15% by mass, and a coating film (y') composed of a composition (y) containing more than 15% by mass of fine particles; Step (2): A step of simultaneously drying the coating film (x') and the coating film (y') formed in step (1). A method for manufacturing an adhesive sheet, which is a method for manufacturing an adhesive sheet as in claim 25, and has at least the following steps (1A) and (2A); step (1A): on the substrate or release material according to the resin And the coating film (xβ') composed of the composition (xβ) with the content of fine particles less than 15% by mass, the coating film (y') composed of the aforementioned composition (y) containing 15% by mass or more of fine particles, and A step of laminating a coating film (xα') composed of a composition (xα) containing a resin with a content of fine particles less than 15% by mass Step; Step (2A): Simultaneously drying the coating film (xβ'), coating film (y'), and coating film (xα') formed in step (1A). A method for manufacturing an adhesive sheet, which is a method for manufacturing an adhesive sheet as in claim 25, and has at least the following steps (1B) and (2B); step (1B): the main part is set on the base material or the release material On the layer (Xβ) containing the resin portion (X), the coating film (y') composed of the aforementioned composition (y) containing 15% by mass or more of fine particles, and the coating film (y') composed of the resin containing the fine particles less than 15 mass % Of the composition (xα) of the coating film (xα') formed in the order of lamination; step (2B): the coating film (y') formed in step (1B) and the coating film ( xα') The step of drying.

Images