KR20170062390A - Pressure-sensitive adhesive sheet and pressure-sensitive adhesive sheet with release film - Google Patents

Abstract

A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer is provided. The pressure-sensitive adhesive sheet has a first surface and a second surface. The first surface is a first adhesive surface constituted by one surface of the pressure-sensitive adhesive layer. The 10-point average roughness of the first adhesive surface is 1000 nm or less. The pressure-sensitive adhesive layer has a storage elastic modulus at 100 占 폚 of 0.08 MPa or more.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive sheet and a release film,

<Cross reference>

This application claims priority to Japanese Patent Application No. 2015-232149, filed on November 27, 2015, and Japanese Patent Application No. 2016-139538, filed on July 14, 2016, The entire contents of which are incorporated herein by reference.

The present invention relates to a pressure-sensitive adhesive sheet and a pressure-sensitive adhesive sheet having a release film.

Generally, a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive, hereinafter the same) shows a state of a soft solid (viscoelastic material) in a temperature region near room temperature and has a property of being easily adhered to an adherend by pressure. Taking advantage of these properties, the pressure-sensitive adhesive is typically used in the form of a pressure-sensitive adhesive sheet including a layer of the pressure-sensitive adhesive, and is widely used in various industrial fields such as automobiles, OA equipment,

In the pressure-sensitive adhesive sheet, a high level of smoothness is required on the pressure-sensitive adhesive surface (surface of the pressure-sensitive adhesive layer). As an example of such a pressure-sensitive adhesive sheet, there can be mentioned a pressure-sensitive adhesive sheet suitable for optical use.

Japanese Patent Application Laid-Open No. 2014-189778 discloses a technical literature on the prevention of the unevenness on the surface of the pressure-sensitive adhesive layer. International Publication No. 2014/156335 is a technical document relating to a double-sided pressure-sensitive adhesive sheet having a release film having a high surface smoothness.

In general, the pressure-sensitive adhesive sheet (in particular, industrial pressure-sensitive adhesive sheet) is often produced by winding a long strip-type pressure-sensitive adhesive sheet in a spiral wound form or a sheet-like form having a relatively large area from the viewpoint of convenience of distribution and productivity . Thereafter, various processes or treatments may be carried out on the pressure-sensitive adhesive sheet, until the pressure-sensitive adhesive sheet is finally attached to the individual adherend. As examples of such processing or processing, there is a method of processing the outer shape of the pressure-sensitive adhesive sheet by punching, cutting or the like to the shape of the adherend, processing for preparing the pressure-sensitive adhesive sheet in a form suitable for efficient and high- .

In the course of such processing or processing, the peeling film for protecting the adhesive surface of the pressure-sensitive adhesive sheet may be exchanged. That is, one peeling film is removed from the adhesive surface of the pressure-sensitive adhesive sheet, and the peeling surface of another peeling film is sometimes bonded to the exposed adhesive surface. Therefore, the release film on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet immediately before adhered to the adherend may be a release film different from the release film on the pressure-sensitive adhesive surface when the pressure-sensitive adhesive sheet is first produced. With the recent diversification of optical products, downsizing, enlargement of screen, improvement of design, and the like, there is a tendency that an opportunity to change the release film on the adhesive surface during the time until the produced pressure sensitive adhesive sheet adheres to the adherend, . However, since the pressure-sensitive adhesive is a viscoelastic material as described above, even if the pressure-sensitive adhesive sheet is originally prepared so as to have a highly smooth pressure-sensitive adhesive surface, the smoothness of the pressure-sensitive adhesive surface may decrease (coarsen) . For example, when the release film protecting the highly smooth adhesive surface is replaced with another release film, the smoothness of the adhesive surface may be lowered depending on the exchangeable release film.

Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive sheet which has a highly smooth adhesive surface and in which the smoothness of the pressure-sensitive adhesive surface is not easily damaged. Another related object is to provide a pressure-sensitive adhesive sheet having a release film having a release film on the pressure-sensitive adhesive surface of such pressure-sensitive adhesive sheet.

The inventors of the present invention have solved the above problems by considering the storage elastic modulus at 100 캜 (storage elastic modulus at 100 캜) of the pressure-sensitive adhesive layer constituting the highly smooth adhesive surface in the pressure-sensitive adhesive sheet having a highly smooth adhesive surface And finally completed the present invention.

According to the present specification, there is provided a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet has a first surface and a second surface. The first surface is a first adhesive surface constituted by one surface of the pressure-sensitive adhesive layer. The 10-point average roughness (Rz _A1 ) of the first adhesive surface is about 1000 nm or less. The pressure-sensitive adhesive layer has a storage elastic modulus (G ' ₁₀₀ ) at 100 ° C of about 0.08 MPa or more. Such a pressure-sensitive adhesive sheet has a highly smooth first adhesive surface, and since the G ' ₁₀₀ of the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface is high, the smoothness of the first pressure-sensitive adhesive surface tends to be hardly damaged. Therefore, the pressure-sensitive adhesive sheet is suitable for applications in which a highly smooth adhesive surface is preferred (for example, optical use).

(G ' ₁₀₀ ) of the pressure-sensitive adhesive layer at a temperature of 100 ° C is about 35% of a storage elastic modulus at 23 ° C (a storage elastic modulus at 23 ° C; G' ₂₃ ) of the pressure-sensitive adhesive layer of the pressure- Or more. That is, the storage modulus ratio (G ' ₁₀₀ / G' ₂₃ ) of the pressure-sensitive adhesive layer at 100 ° C / 23 ° C is about 35% or more. According to the pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer, the performance of maintaining the smoothness of the first pressure-sensitive adhesive surface and the workability of adhesion at room temperature tend to be compatible with each other. The upper limit of G ' ₁₀₀ / G' ₂₃ is not particularly limited, but is usually about 100% or less.

In one form of the technology disclosed herein, 23 ℃ storage modulus (G _'23) of the pressure-sensitive adhesive layer is less than about 0.30MPa. The pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer tends to exhibit good initial adhesion at room temperature.

In one form of the technique disclosed in the present specification, the pressure-sensitive adhesive sheet is such that the second face is a second pressure-sensitive adhesive face. That is, the pressure-sensitive adhesive sheet of this type is constituted as a double-faced pressure-sensitive adhesive sheet in which both the first surface and the second surface are adhesive surfaces. Such a double-sided pressure-sensitive adhesive sheet can be preferably used for the purpose of, for example, bonding or fixing members. In one aspect, the 10-point average roughness (Rz _A2 ) of the second adhesive surface may be about 2000 nm or less (preferably about 1000 nm or less). The double-sided pressure-sensitive adhesive sheet having such a second pressure-sensitive adhesive surface is suitable for applications in which a highly smooth pressure-sensitive adhesive surface is preferred.

In one aspect of the technology disclosed in this specification, the second surface may be a second adhesive surface constituted by the other surface of the pressure-sensitive adhesive layer. That is, one surface and the other surface of the pressure-sensitive adhesive layer constitute the first adhesive surface and the second adhesive surface of the pressure-sensitive adhesive sheet, respectively. This type of pressure-sensitive adhesive sheet has a simple structure and is suitable for improvement of optical characteristics (for example, transparency). In one aspect, the second adhesive surface may have a ten-point average roughness (Rz _A2 ) of the second adhesive surface of about 2000 nm or less (for example, about 1000 nm or less). Such a pressure-sensitive adhesive sheet has a highly smooth second pressure-sensitive adhesive surface, and since the pressure-sensitive adhesive layer constituting the second pressure-sensitive adhesive surface has a high G ' ₁₀₀ , smoothness of the second surface tends to be hardly damaged. Therefore, it is suitable for applications in which highly smooth adhesive surfaces are preferred.

According to this specification, there is also provided a release sheet having a release film comprising any one of the pressure-sensitive adhesive sheets disclosed in this specification and a first release film disposed on the first pressure-sensitive adhesive sheet side of the pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet constituting such a release film-adhered sheet can be preferably used in a form in which the first release film is attached to the adherend through a process of replacing (replacing) the first release film with another release film.

The pressure-sensitive adhesive sheet having a release film having a first release film on the first pressure-sensitive adhesive sheet as described above is characterized in that the ten-point average roughness (Rz _R1 ) of the release face of the first release film contacting the first pressure- It is preferable that the difference in the 10-point average roughness (Rz _A1 ) of the surface is within 250 nm. That is, | Rz _R1 -Rz _A1 | is preferably 250 nm or less. Such a release film-adhered sheet tends to have excellent appearance quality because the adhesion between the release surface of the first release film and the first adhesive surface is good. Hereinafter, the peeling surface in contact with the first adhesive surface may be referred to as &quot; first peeling surface &quot;. The peeling surface in contact with the second adhesive surface may be referred to as &quot; second peeling surface &quot;.

According to the present specification, it is also possible to provide a pressure-sensitive adhesive sheet comprising a double-sided pressure-sensitive adhesive sheet as described in the present specification, a first release film disposed on the first pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet, There is provided a pressure-sensitive adhesive sheet having a release film comprising a second release film. The double-sided pressure-sensitive adhesive sheet constituting such a release film-adhered sheet may be preferably used in a form in which one or both of the first release film and the second release film are exchanged with another release film and adhered to the adherend .

In one preferred form of the pressure-sensitive adhesive sheet (release double-faced pressure-sensitive adhesive sheet with release film) including the double-sided pressure-sensitive adhesive sheet, the first release film and the second release film, the pressure- Wherein the difference between the point average roughness Rz _R1 and the 10 point average roughness Rz _A1 of the first adhesive surface is within 250 nm and the 10 point average roughness Rz _R2 of the second peeling film of the second peeling film And the difference in the 10-point average roughness (Rz _A2 ) of the second adhesive surface may be within 250 nm. That is, | Rz _R1 -Rz _A1 | may be 250 nm or less, and | Rz _R2 -Rz _A2 | may be within 250 nm. The pressure-sensitive adhesive sheet with a release film of this type has a good adhesion between the release surface of the first release film and the first adhesive surface, and adhesion between the release surface of the second release film and the second adhesive surface, have.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing a release sheet-provided pressure-sensitive adhesive sheet including an adhesive sheet (inorganic material double-sided pressure-sensitive adhesive sheet) according to an embodiment.
2 is a schematic cross-sectional view showing a pressure-sensitive adhesive sheet having a release film including a pressure-sensitive adhesive sheet (single-sided pressure-sensitive adhesive sheet with a substrate) according to another embodiment.

Hereinafter, preferred embodiments of the present invention will be described. Further, the matters other than the matters specifically mentioned in this specification are to be understood by those skilled in the art based on the teaching of the invention described in this specification and the technical knowledge at the time of filing of the invention. The present invention can be carried out based on the contents disclosed in this specification and the technical knowledge in the field. In the following drawings, members and parts that exhibit the same function are sometimes given the same reference numerals, and redundant descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematized to clearly illustrate the present invention, and do not necessarily indicate the size and scale of a product actually provided.

As used herein, the term " pressure-sensitive adhesive " refers to a material having a property of showing a state of a soft solid (viscoelastic material) in a temperature region near room temperature and being easily adhered to an adherend by pressure, as described above. The adhesive referred to here generally has a complex tensile modulus E * (1 Hz) &lt; 10 ⁷ , as defined in CA Dahlquist, Adhesion: Fundamental and Practice, McLaren & Sons, dyne / cm &lt; 2 &gt; (typically, a material having the above properties at 25 DEG C).

In the present specification, the term "adhesive surface" means an adhesive surface in which SUS304 stainless steel sheet is adhered to an adherend in accordance with JIS Z0237 (2004), and a 2 kg roller is reciprocated once in a measurement environment at 23 ° C, Refers to a face having a peel strength of 0.1 N / 20 mm or more in the case of peeling in the direction of 180 degrees at a speed of 300 mm / min. In the present specification, the term "non-adhesive surface" refers to a surface not corresponding to the adhesive surface, and typically refers to a surface having a peel strength of less than 0.1 N / 20 mm. The surface (the surface which does not substantially exhibit adhesiveness) which does not adhere to the stainless steel sheet when the 2 kg roller is reciprocated and pressed on the SUS304 stainless steel sheet under the measurement environment at 23 DEG C is included in the concept of the non-adhesive surface It is a typical example.

<Adhesive sheet>

The pressure-sensitive adhesive sheet disclosed in this specification is formed in a sheet-like shape (including a long shape such as a tape shape) having a first surface and a second surface. The pressure-sensitive adhesive sheet includes at least a pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet disclosed in this specification may be constituted by only the pressure-sensitive adhesive layer, or it may comprise constituent elements other than the pressure-sensitive adhesive layer.

The first surface of the pressure-sensitive adhesive sheet disclosed in this specification is an adhesive surface (first adhesive surface) constituted by one surface of the pressure-sensitive adhesive layer. The second surface of the pressure-sensitive adhesive sheet may be an adhesive surface or a non-adhesive surface. In the pressure-sensitive adhesive sheet according to one embodiment, the second surface of the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive surface (second pressure-sensitive adhesive surface) constituted by the other surface of the pressure-sensitive adhesive layer. That is, one surface and the other surface of one pressure-sensitive adhesive layer constitute the first adhesive surface and the second adhesive surface of the pressure-sensitive adhesive sheet, respectively. An example of the configuration of this type of pressure-sensitive adhesive sheet is shown in Fig.

The pressure-sensitive adhesive sheet 1 shown in Fig. 1 is a double-sided pressure-sensitive adhesive sheet of an inorganic material containing a pressure- The first surface 1A of the pressure sensitive adhesive sheet 1 is a first pressure sensitive adhesive surface composed of one surface 11A of the pressure sensitive adhesive layer 11 and the second surface 1B of the pressure sensitive adhesive sheet 1 is a pressure sensitive adhesive layer And the other surface 11B of the first adhesive layer 11. The pressure-sensitive adhesive layer 11 may have a single-layer structure or a multi-layer structure including two or more sub-pressure-sensitive adhesive layers. The constitution (material, thickness, etc.) of the respective sub-pressure-sensitive adhesive layers constituting the multilayer structure may be the same or different. From the viewpoint of productivity and transparency, a mode in which the pressure-sensitive adhesive layer 11 has a single-layer structure can be preferably employed.

Here, the inorganic material double-faced pressure-sensitive adhesive sheet means a double-faced pressure-sensitive adhesive sheet that does not include a non-releasable supporting substrate between the first pressure-sensitive adhesive surface and the second pressure-sensitive adhesive surface. The support substrate refers to a substrate that can maintain its shape independently. In addition, the non-releasable supporting substrate refers to a supporting substrate which is not intended to be separated from the pressure-sensitive adhesive layer during the use period of the pressure-sensitive adhesive sheet including the supporting substrate.

The adhesive sheet 1 before use (that is, before adhering to an adherend) is a sheet having the first adhesive surface 1A and the second adhesive surface 1B, for example, as shown in Fig. 1, The film 21 and the second peel film 22 may be protected. The surface 21A of the first peelable film 21 in contact with the first adhesive surface 11A and the surface 22A of the second peelable film 22 in contact with the second adhesive surface 11B are all peeled off Peelable surface, that is, a surface on which the pressure-sensitive adhesive layer can be peeled from the surface). The pressure sensitive adhesive sheet 1 of this type has a pressure sensitive adhesive sheet 1 and a first release film 21 arranged so as to abut the surface (first release surface) 21A to the first pressure sensitive adhesive surface 11A, And a second release film (22) disposed so as to abut the surface (second release surface) (22A) on the second adhesive surface (12A) And can also be regarded as a component of the mobile terminal 100. The adhesive sheet 100 with a release film may be in the form of a spiral wound. As another mode of the adhesive sheet 1 before use, the release film 22 shown in Fig. 1 is omitted and the release film 21 and the adhesive sheet 21, both of which are the surface 21A and the back surface 21B, The second adhesive surface 11B is brought into contact with the back surface 21B of the peeling film 21 by superimposing the first adhesive layer 1 and winding it in a spiral shape.

Fig. 2 shows an example of the configuration of the adhesive sheet in which the second surface is the non-adhesive surface. The adhesive sheet 2 shown in Fig. 2 includes a supporting substrate 15 having a first surface 15A and a pressure-sensitive adhesive layer 11 disposed on the first surface 15A of the supporting substrate 15 Side single-sided pressure-sensitive adhesive sheet having a base. Here, the first surface 15A of the supporting substrate 15 is a non-peeling surface, that is, a non-peeling surface. The first surface 2A of the adhesive sheet 2 is a first adhesive surface constituted by one surface 11A of the adhesive layer 11 and the second surface 2B of the adhesive sheet 2 is a surface Adhesive surface constituted by the second surface 15B of the second substrate 15. The second surface 15B may be a peeled surface or a non-peeled surface.

The adhesive sheet 2 before use may be in a form in which the first adhesive surface 11A is protected by the first release film 21, for example, as shown in Fig. The pressure sensitive adhesive sheet 2 of this type has a pressure sensitive adhesive sheet 2 and a first release film 21 arranged so that a surface (first release surface) 21A is in contact with the first pressure sensitive adhesive surface 11A, (Single-sided adhesive sheet provided with a release film) 200 including a release film. The release sheet-provided adhesive sheet 200 may be wound in a spiral form.

Another constitutional example of the pressure sensitive adhesive sheet disclosed in this specification is a pressure sensitive adhesive sheet comprising a support base material on both of which a first side and a second side are both unpeelable and having a first pressure sensitive adhesive layer on the first side of the support base, Sensitive adhesive sheet having a base having a second pressure-sensitive adhesive layer on the second surface of the pressure-sensitive adhesive sheet. The double-sided pressure-sensitive adhesive sheet having such a substrate is characterized in that the double-sided pressure-sensitive adhesive sheet has a first surface constituted by the surface of the first pressure-sensitive adhesive layer and a second surface of the double- And a second adhesive surface constituted by the surface. The first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be the same in composition and configuration, or different in composition and / or configuration. Examples of forms in which the compositions of the first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer are the same and the constitution is different from each other include a case where the first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer are pressure sensitive adhesive layers having different thicknesses constituted by the pressure sensitive adhesive composition having the same composition have. Each of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may have a single layer structure, or may have a multilayer structure including two or more sub-pressure-sensitive adhesive layers. From the viewpoint of productivity and transparency, a form in which the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer are both a single-layer structure can be preferably employed.

The double-faced pressure-sensitive adhesive sheet having a base material before use has the same structure as that of the inorganic material double-faced pressure-sensitive adhesive sheet 1 shown in Fig. 1 except that the first pressure-sensitive adhesive surface (the surface of the first pressure- 2 &lt; / RTI &gt; release film. The double-faced pressure-sensitive adhesive sheet having such a base material can be seen as a component of the pressure-sensitive adhesive sheet having the release film including the pressure-sensitive adhesive sheet, the first release film and the second release film. Such a release sheet-equipped pressure-sensitive adhesive sheet may be in the form of a spiral wound. The double-sided pressure-sensitive adhesive sheet having a base material before use may also be in a form in which the release film and both sides of the pressure-sensitive adhesive sheet overlap each other and are rolled up and wound.

In the case of the pressure-sensitive adhesive sheet including the supporting substrate such as the above-described single-sided pressure-sensitive adhesive sheet having the substrate or the double-sided pressure-sensitive adhesive sheet having the substrate, the material of the supporting substrate is not particularly limited. As the supporting substrate, for example, a plastic film, a paper, a woven fabric, a nonwoven fabric, a rubber sheet, a foam sheet, a metal foil, a glass, a composite thereof and the like can be used. The surface of the support substrate on which the pressure-sensitive adhesive layer is provided may be subjected to a surface treatment such as coating with a primer, corona discharge treatment, plasma treatment or the like. In the present specification, the plastic film is typically a non-porous sheet, for example, a concept different from a non-woven fabric (i.e., not including a non-woven fabric).

In one form, various plastic films can be preferably employed as the supporting substrate from those which can easily realize a highly smooth first adhesive surface. Examples of the material of the plastic film include a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, a cellulose resin such as triacetylcellulose, an acetate resin, a polysulfone resin, a polyether sulfone resin, (Meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyamide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin (norbornene resin and the like) Resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, mixtures thereof, and the like. Among them, polyester resin, cellulose resin, polyimide resin and polyether sulfone resin are preferable materials. The plastic film used for the support substrate may be blended with known additives in the same manner as the plastic film for the release film substrate described later. A plastic film having transparency is preferable.

The thickness of the supporting substrate is not particularly limited and can be appropriately selected depending on the purpose. In one form, the thickness of the support substrate may be from about 10 microns to about 500 microns, and typically from about 10 microns to about 300 microns. In one aspect, a support substrate (e.g., the transparent plastic film) having a thickness of about 15 占 퐉 to about 200 占 퐉 may be preferably employed.

(10-point average illumination)

In the pressure-sensitive adhesive sheet disclosed in the present specification, the 10-point average roughness (Rz _A1 ) of the first adhesive surface is preferably about 1000 nm or less. The pressure-sensitive adhesive sheet having such a first pressure-sensitive adhesive surface is preferable for applications in which a highly smooth pressure-sensitive adhesive surface is preferred. For example, the first adhesive surface may be preferably used in the form of being attached to the optical member. In view of providing a smoother adhesive surface, Rz _A1 may preferably be about 700 nm or less, more preferably about 500 nm or less, and more preferably about 300 nm or less (for example, about 200 nm or less). The lower limit of Rz _A1 is not particularly limited. In one form, it may be a Rz _A1 by about 30nm or more (e.g., at least about 50nm).

Here, in the present specification, the 10-point average roughness refers to a 10-point average roughness obtained by using a non-contact type surface roughness measuring apparatus unless otherwise specified. As the non-contact type surface roughness measuring apparatus, an optical interference type surface roughness measuring apparatus is used. As a specific measuring device, Wyko NT-9100 manufactured by Veeco or its equivalent may be used. The concrete measurement operation and measurement conditions can be set in accordance with the measurement conditions described in Examples described later, or the same or similar results as those according to the measurement conditions. The 10-point average roughness was calculated by dividing the height (Yp1 to Yp10) of the top of the mountain from the top of the highest mountain to the tenth top of the mountain and the bottom of the valley from the bottom of the lowest valley to the tenth The elevations Yv1 to Yv10 are measured and obtained as an average value of the absolute values of the differences of Yp1 to Yp10 and Yv1 to Yv10.

In the case where the pressure-sensitive adhesive sheet disclosed in this specification is in the form of a double-sided pressure-sensitive adhesive sheet (i.e., an adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface), the 10 point average roughness Rz _A2 of the second pressure- It is not limited. In one preferred form, Rz _A2 is about 2000nm or less (typically about 1000nm or less, preferably about 700nm or less, more preferably about 500nm or less, more preferably about 300nm or less, such as about 200nm or less ). The lower limit of Rz _A2 is not particularly limited. In one form, Rz _A2 can be at least about 30 nm (e.g., at least about 50 nm). The second adhesive surface may be the other surface of the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface, or may be the surface of the pressure-sensitive adhesive layer different from the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive layer.

(Storage elastic modulus)

In the pressure-sensitive adhesive sheet disclosed in this specification, the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface preferably has a storage elastic modulus (G ' ₁₀₀ ) at 100 ° C of about 0.08 MPa or more. In the pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer, after the production of the pressure-sensitive adhesive sheet, the smoothness of the first pressure-sensitive adhesive surface is hardly damaged. For example, even if the release film on the first adhesive surface is replaced with a lower level of smoothness after the production of the adhesive sheet until the adhesive sheet is adhered to the adherend, deterioration of the smoothness of the first adhesive surface is suppressed . This is because the deformation of the pressure-sensitive adhesive layer after replacement (replacement) of the release film of the pressure-sensitive adhesive sheet once produced is an event that proceeds at low speed. According to the storage elastic modulus at 100 ° C of the pressure- It is possible to properly grasp the behavior of the pressure-sensitive adhesive layer against deformation (time-temperature conversion rule), and by setting the storage elastic modulus at 100 ° C to a predetermined value or more, the smoothness of the first pressure- It is considered that a difficult adhesive sheet is efficiently realized.

In the technique disclosed in this specification, G ' ₁₀₀ may be about 0.09 MPa or more, about 0.10 MPa or more, or about 0.11 MPa or more (for example, about 0.12 MPa or more). By increasing G ' ₁₀₀ , the smoothness of the first adhesive surface tends to be kept better. The upper limit of G ' ₁₀₀ is not particularly limited, and may be, for example, about 1.5 MPa or less (typically about 1.0 MPa or less). From the viewpoint of adhesion to an adherend, G ' ₁₀₀ is usually suitably less than about 0.50 MPa, preferably less than about 0.40 MPa, and more preferably less than about 0.30 MPa. G ' ₁₀₀ is a value obtained by measuring the composition of the pressure-sensitive adhesive layer (for example, the composition and molecular weight of the polymer contained in the pressure-sensitive adhesive layer, the type of crosslinking, the crosslinking density, the use of additives, .

In one form of the technology disclosed herein, it can be a 23 ℃ of the pressure-sensitive adhesive layer constituting the first adhesive surface of the adhesive sheet The storage elastic modulus (G _'23) to less than about 0.30MPa. The pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer tends to exhibit good initial adhesion to the adherend at room temperature. This is preferable from the viewpoints of workability (for example, working efficiency and adhesion accuracy) of the adhesive sheet. In one form, G 'is _23, it is possible to approximately 0.29MPa or less, and even up to about 0.27MPa, or may be up to about 0.25MPa. By lowering the G _'23, there is a tendency that the initial adhesion of the adhesive sheet is improved. The lower limit of G _'23 is not particularly limited, for example, at least about 0.05MPa. "From the viewpoint of facilitating the balance of the _100, typically, G 'is G ₂₃ or more predetermined, suitably at least about 0.08MPa to about 0.10MPa or more are preferred, at least about 0.15MPa (e.g. at least about 0.17MPa ) Is more preferable. G 'is _23, it can be adjusted by the composition of the pressure-sensitive adhesive layer and the method of manufacturing the same.

The storage elastic modulus (G ' ₁₀₀ ) at 100 ° C and the storage elastic modulus at 23 ° C (G' ₂₃ ) of the pressure-sensitive adhesive layer in the present invention are not particularly limited as long as the pressure- Values of storage modulus at 100 占 폚 and 23 占 폚 can be used. As a specific measuring device, ARES manufactured by TA Instrument or its equivalent can be used. The concrete measurement operation and measurement conditions can be set in accordance with the measurement conditions described in Examples described later, or the same or similar results as those according to the measurement conditions.

The technique disclosed in this specification is a technique in which the pressure-sensitive adhesive layer constituting the first adhesive surface has a storage modulus ratio (G ' ₁₀₀ / G' ₂₃ ) at 100 ° C / 23 ° C of more than about 30% (for example, about 31% Or the like. G ' ₁₀₀ / G' ₂₃ can be about 35% or more, about 40% or more, and more preferably about 40% or more, from the viewpoint of more desirably balancing both the performance of maintaining the smoothness of the first adhesive surface and the workability at room temperature , About 50% or more (for example, about 55% or more). The upper limit of G ' ₁₀₀ / G' ₂₃ is not particularly limited, but is usually about 100% or less, typically about 100% or less. G ' ₁₀₀ / G' ₂₃ may be about 90% or less and about 80% or less (for example, about 70% or less) from the viewpoint of further improving the workability at room temperature. In one form, G ' ₁₀₀ / G' ₂₃ can be from about 35% to about 50%. Such a pressure-sensitive adhesive layer tends to form a highly smooth first adhesive surface.

In one aspect of the technology disclosed in the present specification, the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface has a ratio of a storage elastic modulus at 100 ° C (G ' ₁₀₀ ) to a thickness (T _A1 ) . Thus, G 'pressure-sensitive adhesive sheet that is ₁₀₀ / T _A1 having a pressure-sensitive adhesive layer is not more than the predetermined value, than the G' is preferably ₁₀₀ / T _A1 is larger than the pressure-sensitive adhesive layer, the long-term as they tend to see the exhibits good adhesion. For example, G _'100 is at least about 0.08MPa (typically, less than about at least about 0.08MPa 0.50MPa), and also G' on the pressure-sensitive adhesive layer according to the ₁₀₀ / T _A1 is less than or equal to about 9MPa / mm, the first adhesive surface Even when the release film is exchanged for a lower smoothness, the pressure-sensitive adhesive sheet which is hardly damaged in smoothness of the first pressure-sensitive adhesive surface and which has excellent long-term adhesion to the adherend can be realized. In one aspect, G ' ₁₀₀ / T _A1 can be set to about 7.0 MPa / mm or less from the viewpoint of obtaining a better effect. The techniques disclosed herein can be preferably implemented, for example, in the form that G ' ₁₀₀ / T _A1 is less than or equal to about 5.0 MPa / mm (e.g., less than or equal to about 3.0 MPa / mm). The lower limit of G ' ₁₀₀ / T _A1 is not particularly limited, but it is usually suitably about 0.1 MPa / mm or more.

In the technique disclosed in this specification, the thickness (T _A1 ) of the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface is not particularly limited. T _A1 may be, for example, from about 1 μm to about 500 μm (typically from about 1 μm to about 250 μm). In one aspect, T _A1 may be about 5 탆 or more, or about 15 탆 or more. When T _A1 is increased, the peeling film on the first adhesive surface tends to undergo smooth degradation of smoothness of the first adhesive surface due to exchange of the film with low smoothness. For this reason, the significance of suppressing the decrease in smoothness of the first adhesive surface is greater by applying the technique disclosed in this specification. In this regard, the techniques disclosed herein are preferred in a form where T _A1 is greater than about 20 microns (more preferably greater than about 25 microns, and more preferably greater than about 30 microns, such as greater than about 40 microns) . In addition, when T _A1 becomes smaller, the influence of the smoothness of the first adhesive surface on the characteristics of the entire adhesive sheet tends to become larger. From this viewpoint, the technique disclosed in this specification can be preferably implemented in a form in which T _A1 is about 250 탆 or less (more preferably about 150 탆 or less, for example, about 100 탆 or less). In one aspect, T _A1 may be about 60 μm or less (eg, about 50 μm or less).

In one form of the technology disclosed herein, the first pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive surface, the art the thickness of the adhesive layer (T _A1) 23 ℃ storage modulus (G _'23) ratio of about 10MPa / mm is less than for the . As described above, the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer having G _'23 / T _A1 less than the predetermined value tends to exhibit better initial adhesion to the adherend as compared with the pressure-sensitive adhesive layer having a larger G' ₂₃ / T _A1 . For example, according to the pressure-sensitive adhesive layer having a G ' ₁₀₀ of about 0.08 MPa or more (typically about 0.08 MPa or more and less than about 0.50 MPa) and G' ₂₃ / T _A1 of about 10 MPa / mm or less, Even when the release film is exchanged for a lower smoothness, the smoothness of the first pressure-sensitive adhesive surface is hardly damaged and the pressure-sensitive adhesive sheet having excellent initial adhesion to the adherend can be realized. In view of obtaining a better effect, in one form, it may be a G _'23 / T _A1 to about 8.0MPa / mm. Technology described herein, for example, G _'23 / T are _A1 can be preferably carried out in the form of up to about 6.0MPa / mm (e.g. up to about 5.0MPa / mm). The lower limit of G _'23 / T _A1 is not particularly limited, but usually it is suitably at least about 0.2 MPa / mm.

In the case where the pressure-sensitive adhesive sheet disclosed in this specification is in the form of a double-sided pressure-sensitive adhesive sheet, the second pressure-sensitive adhesive surface may be the other surface of the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface. Such a double-sided pressure-sensitive adhesive sheet (inorganic double-sided pressure-sensitive adhesive sheet) has a simple structure and is suitable for improvement of optical properties (for example, transparency). The second adhesive surface may also be a surface of a pressure-sensitive adhesive layer different from the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface, that is, the surface of the second pressure-sensitive adhesive layer. The double-sided pressure-sensitive adhesive sheet of this type typically takes the form of a double-sided pressure-sensitive adhesive sheet having a substrate, and various performances are realized by the combination of the composition and constitution of the first pressure-sensitive adhesive layer and the second pressure- . In one aspect, the second pressure sensitive adhesive layer may have various properties (for example, G ' ₁₀₀ , G' ₂₃ , G ' ₁₀₀ / G' ₂₃ , T _A1 , G ' ₁₀₀ / T _A1 , G' ₂₃ / T _A1 , a haze value, etc.).

<Adhesive>

In the technique disclosed in this specification, the kind of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited. For example, known adhesives such as acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives (natural rubber, synthetic rubber, mixtures thereof, etc.), silicone pressure sensitive adhesives, polyester pressure sensitive adhesives, urethane pressure sensitive adhesives, polyether pressure sensitive adhesives, polyamide pressure sensitive adhesives, And a pressure-sensitive adhesive layer comprising one or more kinds of pressure-sensitive adhesives selected from various pressure-sensitive adhesives. Here, the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a (meth) acryl-based polymer as a base polymer (a main component in the polymer component, that is, a component exceeding 50 mass%). The same applies to rubber-based pressure-sensitive adhesives and other pressure-sensitive adhesives. From the viewpoints of transparency and weatherability, preferred examples of the pressure-sensitive adhesive layer include a pressure-sensitive adhesive layer in which the content of the acrylic pressure-sensitive adhesive is 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more. The content of the acrylic pressure-sensitive adhesive may be more than 98% by weight, or may be a pressure-sensitive adhesive layer substantially containing an acrylic pressure-sensitive adhesive.

In the present specification, the term &quot; (meth) acryl &quot; means a generic term for acrylic and methacrylic. Likewise, "(meth) acryloyl" means acryloyl and methacryloyl, and "(meth) acrylate" means acrylate and methacrylate, respectively.

In the present specification, the (meth) acryl-based polymer refers to a polymer containing a (meth) acryl-based monomer as a monomer component constituting the (meth) acryl-based polymer. That is, it refers to a polymer containing a monomer unit derived from a (meth) acrylic monomer. Here, (meth) acrylic monomers are monomers having at least one (meth) acryloyl group in one molecule.

Although not particularly limited, in one form of the technology disclosed in this specification, the pressure-sensitive adhesive layer can be suitably prepared using a pressure-sensitive adhesive composition comprising a monomer component constituting the (meth) acrylic polymer. Hereinafter, such a pressure-sensitive adhesive composition may be referred to as "(meth) acrylic pressure-sensitive adhesive composition". Here, the "monomer component constituting the (meth) acrylic polymer" refers to a monomer component constituting the (meth) acrylic polymer in the pressure-sensitive adhesive obtained from the (meth) acrylic pressure sensitive adhesive composition. The monomer component may be contained in the (meth) acrylic pressure sensitive adhesive composition as an unreacted monomer (that is, in the form of a raw material monomer in which a polymerizable functional group is unreacted) or in the form of a polymer (i.e., as a monomer unit) Or both of them may be included.

&Lt; Monomer component >

In one aspect of the technology disclosed in this specification, the pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition comprising the following component (A) as a monomer component constituting the (meth) acrylic polymer. In one preferred form, the pressure-sensitive adhesive layer contains at least the following component (A) as a monomer component constituting the (meth) acryl-based polymer and, if necessary, the following component (B) (Meth) acrylic pressure-sensitive adhesive composition, which further comprises one or both of the above-mentioned components.

(Component (A))

The component (A) is an alkyl (meth) acrylate having an alkyl group having 2 to 18 carbon atoms at the terminal of the ester. Hereinafter, the alkyl (meth) acrylate having an alkyl group having an alkyl group of X to Y at the terminal of the ester may be referred to as &quot; C _{X -Y} alkyl (meth) acrylate &quot;. The structure of the C _2-18 alkyl group in the C _{2 -18} alkyl (meth) acrylate is not particularly limited, and any of those in which the alkyl group is linear or branched may be used. As the component (A), one such C _2-18 alkyl (meth) acrylate may be used alone or in combination of two or more.

A straight-chain alkyl group as a C _2-18 alkyl (meth) acrylate having a terminal ester, (meth) acrylate, n- propyl (meth) acrylate, n- butyl (meth) acrylate, n- pentyl (meth) Acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (Meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, Hexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate and n-octadecyl (meth) acrylate. _{Examples of the C3-18} alkyl (meth) acrylate having a branched alkyl group at the terminal of the ester include isopropyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (Meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) acrylate, isohexyl (meth) acrylate, (Meth) acrylate, isododecyl (meth) acrylate, isododecyl (meth) acrylate, isododecyl (meth) acrylate, (Meth) acrylate, isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isomyristyl (meth) acrylate, isomyristyl ) Acrylate and the like It is poetry. The technique disclosed in this specification can be preferably implemented in a form in which the component (A) includes one or more selected from C _4-9 alkyl acrylates. Suitable examples of the C _{4 -9} alkyl acrylate include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate and isononyl acrylate.

(Component (B)).

The component (B) is an alicyclic monomer. In a mode of using the component (B) in combination with the component (A), a pressure-sensitive adhesive (a pressure-sensitive adhesive) which satisfies balance between the storage elastic modulus and the adhesive properties (for example, adhesiveness to an adherend) Layer can be preferably realized.

As the alicyclic monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having an alicyclic structure-containing group can be used without particular limitation. As the component (B), one of these alicyclic monomers may be used alone or two or more of them may be used in combination. Here, the "alicyclic structure-containing group" refers to a moiety containing at least one alicyclic structure. The term "alicyclic structure" refers to a saturated or unsaturated carbon ring structure having no aromaticity. In this specification, the alicyclic structure-containing group may be simply referred to as an &quot; alicyclic group &quot;. Suitable examples of the alicyclic group include a hydrocarbon group and hydrocarbonoxy group containing an alicyclic structure.

Examples of preferred alicyclic monomers in the art disclosed in the present specification include alicyclic (meth) acrylates having an alicyclic group and a (meth) acryloyl group. Specific examples of the alicyclic (meth) acrylate include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl , HPMPA, TMA-2 and HCPA represented by the following formulas, in addition to cyclooctyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

The number of carbon atoms in the alicyclic group in the alicyclic monomer (in the case of alicyclic (meth) acrylate, the part excluding the (meth) acryloyl group from the alicyclic (meth) acrylate) is not particularly limited. For example, an alicyclic monomer having 4 to 24 (preferably 5 to 18, more preferably 5 to 12) carbon atoms in the alicyclic group can be used. Among them, cyclohexyl acrylate (CHA), cyclohexyl methacrylate, isobornyl acrylate (IBXA) and isobornyl methacrylate are preferable, CHA and IBXA are more preferable, and CHA is particularly preferable.

(Component (C)) [

The component (C) is a monomer having at least any one of a hydroxyl group and a carboxyl group.

As the hydroxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. The hydroxyl group-containing monomers may be used singly or in combination of two or more. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl Hydroxyalkyl (meth) acrylates such as hydroxyaryl (meth) acrylate and the like; (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and other hydroxyalkylcycloalkane (meth) acrylates. Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. Of these, hydroxyalkyl (meth) acrylates are preferred. For example, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 6 carbon atoms can be preferably used. In one preferred form, a copolymer of one kind selected from 2-hydroxyethyl acrylate (2HEA), 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate (4HBA), and 4-hydroxybutyl methacrylate Or two or more of them may be used as the hydroxyl group-containing monomer. The hydroxy group containing monomer used in the preferred form of the technique disclosed herein may be 4HBA alone, 2HEA alone, or a combination of 4HBA and 2HEA.

As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. The carboxyl group-containing monomers may be used singly or in combination of two or more. Examples of the carboxyl group-containing monomers include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate; Ethylenically unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid and citraconic acid; Metal salts thereof (for example, alkali metal salts); And anhydrides of the ethylenically unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.

The technique disclosed in this specification is preferably carried out in a form in which the component (C) comprises a hydroxyl group-containing monomer. That is, it is preferable that the component (C) contains only the hydroxyl group-containing monomer, or contains the hydroxyl group-containing monomer and the carboxyl group-containing monomer. When the component (C) comprises a hydroxyl group-containing monomer and a carboxyl group-containing monomer, the proportion of the hydroxyl group-containing monomer in the entire component (C) is preferably more than about 50% by weight, more preferably about 80% More preferably about 90% by weight or more). The proportion of the hydroxyl group-containing monomer in the component (C) is preferably increased from the viewpoint of reducing metal corrosion due to carboxyl groups and the like. The technique disclosed in this specification can be preferably carried out in a form in which the monomer component does not substantially contain a monomer containing a carboxyl group. For example, the proportion of the carboxyl group-containing monomer in the monomer component may be less than about 1% by weight, preferably less than about 0.5% by weight, more preferably less than about 0.2% by weight.

The proportion of the component (A) in the entire monomer component is not particularly limited. G _'100 and G' ₁₀₀ / G 'from such a pressure-sensitive adhesive layer is one or both of ₂₃ which is the desired value will tend to be obtained, the ratio of the component (A), or less suitable, and about 85 about 90% by weight By weight or less, more preferably about 70% by weight or less. In a preferred form, the proportion of component (A) may be less than or equal to about 60% by weight (more preferably less than or equal to about 50% by weight, for example less than about 50% by weight). From the viewpoint of initial adhesion to the adherend, the proportion of the component (A) is preferably at least about 30% by weight, and more preferably at least about 35% by weight. In one form, the proportion of the component (A) in the entire monomer component may be, for example, about 30 to 70% by weight.

When the component (B) is contained as the monomer component, the proportion of the component (B) in the entire monomer component is not particularly limited. From the G _'100 and G' ₁₀₀ / G 'pressure-sensitive adhesive layer is one or both of ₂₃ which is the preferred value would tend to foul the like, the proportion of the component (B) is, usually, suitably approximately 3% by weight or more, and And more preferably about 5% by weight or more, and more preferably about 8% by weight or more (for example, about 10% by weight or more). The proportion of the component (B) is suitably about 65% by weight or less, preferably about 60% by weight or less, more preferably about 55% by weight or less (more preferably about 50% By weight or less, for example, less than about 50% by weight). In a preferred form, the proportion of the component (B) in the entire monomer component may be at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, and more preferably at least about 30 wt% For example, about 35% by weight or more). In one form, the proportion of the component (B) in the entire monomer component may be, for example, about 20 to 50% by weight.

When the component (C) is contained as the monomer component, the proportion of the component (C) in the entire monomer component is not particularly limited. The proportion of the component (C) is typically at least about 3% by weight, preferably at least about 5% by weight, and more preferably at least about 8% by weight (for example, about More preferably 10% by weight or more). In addition, G _'100 and G' ₁₀₀ / G 'from such a pressure-sensitive adhesive layer is one or both of ₂₃ which is the preferred value will tend to be obtained, the ratio of the component (C), and not more than about 35% by weight, preferably, More preferably about 30% by weight or less, and still more preferably about 25% by weight or less. In one form, the ratio of the component (C) may be, for example, about 15 to 30% by weight.

(Optional monomers)

The monomer components in the techniques disclosed in this specification may contain monomers other than the components (A), (B) and (C) described above (hereinafter, also referred to as "optional monomers").

Examples of such optional monomers include heterocyclic ring-containing monomers such as cyclic nitrogen-containing monomers and cyclic ether group-containing monomers. Such a heterocyclic ring-containing monomer can contribute to the realization of a pressure-sensitive adhesive layer that balances both the desirable storage elastic modulus and other adhesive properties or other characteristics described in this specification similarly to the above-mentioned component (B). Further, it can also help to improve the adhesion and cohesion of the adhesive. The heterocyclic ring-containing monomers may be used singly or in combination of two or more.

As the cyclic nitrogen-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of the cyclic nitrogen-containing monomer include lactam-based vinyl monomers such as N-vinylpyrrolidone, N-vinyl-epsilon -caprolactam and methylvinylpyrrolidone; Oxazoline group-containing monomers such as 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline and 2-isopropenyl-2-oxazoline; And vinyl-based monomers having a nitrogen-containing heterocycle such as vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole and vinylmorpholine. Other examples of the cyclic nitrogen-containing monomers include (meth) acrylic monomers containing nitrogen-containing heterocyclic rings such as morpholine ring, piperidine ring, pyrrolidine ring, piperazine ring and aziridine ring. Specific examples thereof include N-acryloyl morpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and N-acryloyl aziridine. Of the cyclic nitrogen-containing monomers, lactam-based vinyl monomers are preferable in view of cohesiveness and the like, and N-vinyl pyrrolidone is more preferable.

As the monomer having a cyclic ether group, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a cyclic ether group such as an epoxy group or an oxetane group can be used without particular limitation. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether have. Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl , 3-butyl-oxetanylmethyl (meth) acrylate, 3-hexyl-oxetanylmethyl (meth) acrylate and the like.

As another example of the optional monomers, alkyl (meth) acrylates which are not included in the component (A), that is, alkyl (meth) acrylates having 1 or more carbon atoms (for example, 19 to 24) have. Specific examples of such alkyl (meth) acrylates include methyl (meth) acrylate, n-nonadecyl (meth) acrylate, isononadecyl (meth) acrylate, n-eicosyl (Meth) acrylate, and the like. These may be used singly or in combination of two or more.

Other examples of the optional monomers include monomers containing a functional group other than a hydroxyl group and a carboxyl group. These functional group-containing monomers can be used for the purpose of introducing crosslinking points into the (meth) acrylic polymer or enhancing the cohesive force of the (meth) acrylic polymer. Examples of the functional group-containing monomer include amide group-containing monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; For example, cyano group-containing monomers such as acrylonitrile and methacrylonitrile; Sulfonic acid group-containing monomers such as styrenesulfonic acid, allylsulfonic acid and 2- (meth) acrylamide-2-methylpropanesulfonic acid; Monomers containing phosphoric acid groups such as 2-hydroxyethyl acryloyl phosphate and the like; Examples thereof include keto-containing monomers such as diacetone (meth) acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, and vinyl acetoacetate; Isocyanate group-containing monomers such as 2- (meth) acryloyloxyethyl isocyanate; Alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Alkoxysilyl group-containing monomers such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane; And the like. These may be used singly or in combination of two or more.

(A), (B), and (C) as the optional monomer for the purpose of adjusting the Tg of the (meth) acryl-based polymer and improving the cohesive strength, And may include copolymerizable monomers other than those exemplified above. Examples of such copolymerizable monomers include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyl compounds such as styrene, substituted styrene (? -Methylstyrene and the like) and vinyltoluene; (Meth) acrylates, such as aryl (meth) acrylates (e.g., phenyl (meth) acrylate), aryloxyalkyl (meth) (Meth) acrylate); aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate; For example, olefinic monomers such as ethylene, propylene, isoprene, butadiene and isobutylene; Chlorine-containing monomers such as vinyl chloride and vinylidene chloride; Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; Other examples include macromonomers having a radical polymerizable vinyl group at the end of a monomer polymerized with a vinyl group. These may be used singly or in combination of two or more.

The amount of the optional monomer to be used is not particularly limited and can be appropriately determined. In general, the total amount of optional monomers used is suitably less than about 50% by weight of the monomer component, preferably about 30% by weight or less, more preferably about 20% by weight or less. The techniques disclosed herein can preferably be implemented in a form wherein the total usage of any monomer is no more than about 10 weight percent (e.g., no more than about 5 weight percent) of the monomer component. When an arbitrary monomer is used, from the viewpoint of appropriately exhibiting the effect of increasing the adhesive force or the cohesive force, it is appropriate that the amount of the optional monomer is set to about 0.5% by weight or more of the monomer component and more preferably about 0.8% desirable. Also, the techniques disclosed herein are also preferably in a form that does not substantially utilize any monomers (e.g., where the amount of optional monomers is about 0.3% by weight or less, typically about 0.1% by weight or less of the monomer component) .

The aforementioned components (A), (B), (C) and optional monomers are typically monofunctional monomers. The monomer component may contain, in addition to such a monofunctional monomer, an appropriate amount of a polyfunctional monomer for the purpose of adjusting the storage modulus of the pressure-sensitive adhesive layer and the like. Herein, the monofunctional monomer refers to a monomer having only one polymerizable functional group (typically, a radically polymerizable functional group) having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. In contrast, the multifunctional monomer refers to a monomer having at least two such polymerizable functional groups as described later.

(Polyfunctional monomer)

The multifunctional monomer is a monomer having at least two polymerizable functional groups (typically, a radically polymerizable functional group) having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,4 (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri Esters of polyhydric alcohols and (meth) acrylic acid such as (meth) acrylate; Vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Suitable examples of these include trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Among them, 1,6-hexanediol di (meth) acrylate is preferable. The polyfunctional monomer may be used singly or in combination of two or more. From the standpoint of reactivity and the like, a polyfunctional monomer having two or more acryloyl groups is usually preferable.

The amount of the multifunctional monomer to be used is not particularly limited and may be suitably set so that the intended use of the multifunctional monomer can be achieved. From the viewpoint of balancing favorable storage elastic modulus and other adhesive properties or other properties disclosed in the present specification, the amount of the polyfunctional monomer to be used may be about 3% by weight or less of the monomer component in one form, 2% by weight or less, and more preferably about 1% by weight or less (for example, about 0.5% by weight or less). When the polyfunctional monomer is used, the lower limit of the amount to be used may be larger than 0% by weight and is not particularly limited. Generally, by using the multifunctional monomer in an amount of about 0.001% by weight or more (for example, about 0.01% by weight or more) of the monomer component, the effect of using the multifunctional monomer can be properly exerted.

The proportion of the total amount of the component (A), the component (B) and the component (C) in the entire monomer component is typically about 50% by weight or more, preferably about 70% by weight or more , More preferably at least about 80 wt%, and even more preferably at least about 90 wt%. The techniques disclosed herein can preferably be implemented in a form wherein the ratio of the total amount is at least about 95% by weight (e.g., at least about 99% by weight). The ratio of the total amount may be 100 wt%. The technique disclosed in this specification can be preferably carried out in a form in which the ratio of the total amount of the monomer components to the entire monomer components is 99.999% by weight or less (for example, 99.99% by weight or less).

The Tg of the copolymer corresponding to the composition of the monomer component is preferably approximately -20 占 폚 or lower, more preferably approximately -25 占 폚 or lower, from the viewpoints of adhesiveness of the pressure-sensitive adhesive sheet and low- Do. In addition, G and the like from the _'100 and G' ₁₀₀ / G 'pressure-sensitive adhesive layer is one or both of ₂₃ which is the preferred value of an easy be obtained, the Tg of the copolymer is suitably not less than about -55 ℃, approximately - More preferably 50 ° C or higher, and more preferably approximately -45 ° C or higher. The techniques disclosed in this specification can be preferably implemented also in the form that the Tg of the copolymer is approximately -40 캜 or higher (for example, approximately -35 캜 or higher).

Here, the Tg of the copolymer corresponding to the composition of the monomer component means the Tg determined by Fox's formula based on the composition of the monomer component. The formula of Fox is a relational expression of the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as described below.

1 / Tg =? (Wi / Tgi)

In the Fox equation, Tg is the glass transition temperature (unit: K) of the copolymer, Wi is the weight fraction (copolymerization ratio based on weight) of the monomer i in the copolymer, Tgi is the homo- And the glass transition temperature (unit: K) of the polymer. However, in the present specification, the calculation of Tg is made only in consideration of the monofunctional monomer. Therefore, when the monomer component comprises a polyfunctional monomer, the total amount of the monofunctional monomers contained in the monomer component is 100% by weight, and the Tg of the homopolymer of each monofunctional monomer and the total amount of the monofunctional monomer The Tg is calculated based on the weight fraction of the water-soluble polymer.

As the glass transition temperature of the homopolymer used for the calculation of Tg, the values described in the known data are to be used. For example, for the following monomers, the following values are used as the glass transition temperature of the homopolymer of the monomer.

n-butyl acrylate -55 ° C

2-ethylhexyl acrylate -70 ° C

Cyclohexyl acrylate  15 ℃

Isobornyl acrylate  94 ° C

2-hydroxyethyl acrylate -15 ℃

4-hydroxybutyl acrylate -40 ° C

Acrylic acid 106 ° C

Methacrylic acid 228 ° C

For the glass transition temperature of the homopolymer of the monomers other than those exemplified above, the numerical values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc, 1989) are used. The highest value is adopted for the monomers in which plural kinds of values are described in this document.

For the monomers for which the glass transition temperature of the homopolymer is not described in the above-mentioned &quot; Polymer Handbook &quot;, a value obtained by the following measuring method is used (see Japanese Patent Application Laid-Open No. 2007-51271). Specifically, 100 parts by weight of a monomer, 0.2 part by weight of azobisisobutyronitrile and 200 parts by weight of ethyl acetate as a polymerization solvent were fed into a reactor equipped with a thermometer, a stirrer, a nitrogen introduction pipe and a reflux condenser, Stir for 1 hour while circulating. After the oxygen in the polymerization system was removed in this way, the temperature was raised to 63 캜 and the reaction was carried out for 10 hours. Subsequently, the solution is cooled to room temperature to obtain a homopolymer solution having a solid concentration of 33% by weight. This homopolymer solution is applied on a release film in a pliable form and dried to produce a test sample (homopolymer of sheet form) having a thickness of about 2 mm. This test sample was punched into a disk having a diameter of 7.9 mm, sandwiched between parallel plates, and subjected to shear deformation at a frequency of 1 Hz using a viscoelasticity tester (ARES, manufactured by TA Instruments) , The viscoelasticity is measured by the shearing mode at a heating rate of 5 DEG C / min, and the peak top temperature of tan delta (loss tangent) is taken as the glass transition temperature.

&Lt; Pressure sensitive adhesive composition &

The pressure-sensitive adhesive layer disclosed in the present specification can be produced by using a pressure-sensitive adhesive composition comprising a monomer component of the composition as described above in the form of a polymerized product, a non-polymerized product (i.e., a form in which a polymerizable functional group is unreacted) . The pressure-sensitive adhesive composition includes a composition (solvent-type pressure-sensitive adhesive composition) containing a pressure-sensitive adhesive (pressure-sensitive adhesive component) in an organic solvent, a composition in which the pressure-sensitive adhesive is dispersed in an aqueous solvent (Active energy ray-curable pressure-sensitive adhesive composition) prepared by curing by means of a wire to form a pressure-sensitive adhesive, a hot-melt type pressure-sensitive adhesive composition which is applied in a heated and melted state and forms an adhesive when cooled to near room temperature. have.

In this specification, the term &quot; active energy ray &quot; refers to an energy ray having an energy capable of causing a chemical reaction such as polymerization reaction, crosslinking reaction, decomposition of an initiator, and the like. Examples of the active energy ray include rays such as ultraviolet rays, visible rays, and infrared rays, and radiation such as? Rays,? Rays,? Rays, electron rays, neutron rays, and X rays.

Typically, the pressure-sensitive adhesive composition includes at least a part of monomer components (may be part of the kind of monomer or part of the amount) of the monomer composition of the composition in the form of a polymer. The polymerization method for forming the polymer is not particularly limited and various conventionally known polymerization methods can be suitably employed. For example, thermal polymerization such as solution polymerization, emulsion polymerization, bulk polymerization and the like (typically performed in the presence of a thermal polymerization initiator); Photopolymerization (typically, in the presence of a photopolymerization initiator) performed by irradiating light such as ultraviolet rays; irradiation with radiation such as? rays,? rays or the like; And the like can be appropriately adopted. Among them, photopolymerization is preferable. In this polymerization method, the form of the polymerization is not particularly limited, and the polymerization conditions (temperature, time, pressure, light amount, irradiation dose, etc.), materials used other than the monomer (polymerization initiator, surfactant, etc.) ) Can be appropriately selected and performed.

In polymerization, known or publicly known photopolymerization initiators or thermal polymerization initiators may be used depending on the polymerization method, polymerization type, and the like. These polymerization initiators may be used singly or in combination of two or more.

Examples of the photopolymerization initiator include, but are not limited to, ketal based photopolymerization initiators, acetophenone based photopolymerization initiators, benzoin ether based photopolymerization initiators, acylphosphine oxide based photopolymerization initiators, An aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, etc. .

Specific examples of the ketal-based photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one (for example, trade name "Irgacure 651" manufactured by BASF).

Specific examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexyl-phenyl-ketone (e.g., Irgacure 184, trade name, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t Butyl-dichloroacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 2-methyl-1-phenyl-propan-1-one (trade name "DARACURE 1173" manufactured by BASF Corporation), methoxyacetophenone, and the like do.

Specific examples of the benzoin ether-based photopolymerization initiator include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Substituted benzoin ethers.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (e.g., Irgacure 819, a product of BASF), bis 4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, trade name "Lucirin TPO ), Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.

Specific examples of the? -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1- do. Specific examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride and the like. Specific examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like. Specific examples of the benzoin-based photopolymerization initiator include benzoin and the like. Specific examples of the benzylic photopolymerization initiator include benzyl and the like.

Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone,? -Hydroxycyclohexyl phenyl ketone and the like.

Specific examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichloro Thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

The thermal polymerization initiator is not particularly limited, and for example, an azo-based polymerization initiator, a peroxide-based initiator, a redox-based initiator by a combination of a peroxide and a reducing agent, and a substituted ethane-based initiator may be used. More specifically, there may be mentioned, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylpropionamidine) Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis Azo-based initiators such as 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate; Persulfates such as potassium persulfate and ammonium persulfate; Peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide; Substituted ethane-based initiators such as phenyl-substituted ethane; Redox initiators such as a combination of persulfate and sodium hydrogen sulfite, a combination of peroxide and sodium ascorbate, and the like; And the like, but are not limited thereto. Further, the thermal polymerization can be preferably carried out at a temperature of, for example, about 20 to 100 占 폚 (typically 40 to 80 占 폚).

The amount of such a thermal polymerization initiator or photopolymerization initiator to be used may be a usual amount to be used depending on the polymerization method, polymerization type, and the like, and is not particularly limited. For example, about 0.001 to 5 parts by weight (typically about 0.01 to 2 parts by weight, for example, about 0.01 to 1 part by weight) of a polymerization initiator may be used per 100 parts by weight of the monomer to be polymerized.

(A pressure-sensitive adhesive composition comprising a polymerizable compound and a non-polymerizable compound)

The pressure-sensitive adhesive composition according to one preferred form comprises a polymerization reaction of a monomer mixture comprising at least a part of the monomer components (raw monomers) of the composition. Typically, some of the monomer components are included in the form of polymerizates and the remainder are included in the form of un-polymerized (unreacted monomers). The polymerization reaction of the monomer mixture can be prepared by at least partially polymerizing the monomer mixture.

The polymerization reactant is preferably a partial polymer of the monomer mixture. These partial polymerizates are mixtures of polymerized and unreacted monomers derived from the monomer mixture, and typically exhibit syrup-like (liquid with a viscosity). Hereinafter, the partial polymer of such properties may be referred to as &quot; monomer syrup &quot; or simply &quot; syrup &quot;.

The polymerization method for obtaining the polymerization reaction product is not particularly limited, and various polymerization methods can be appropriately selected and used as described above. From the viewpoints of efficiency and simplicity, the photopolymerization method can be preferably employed. According to the photopolymerization, the polymerization conversion rate of the monomer mixture can be easily controlled by the polymerization conditions such as the irradiation amount (light amount) of light.

The polymerization conversion rate (monomer conversion) of the monomer mixture in the partial polymer is not particularly limited. The polymerization conversion rate may be, for example, about 70% by weight or less, and preferably about 60% by weight or less. In general, the polymerization conversion rate is suitably about 50% by weight or less, preferably about 40% by weight or less (for example, about 35% by weight or less), from the viewpoints of ease of preparation, application workability and the like of the pressure- . The lower limit of the polymerization conversion rate is not particularly limited, but is typically about 1% by weight or more, and usually about 5% by weight or more.

The pressure-sensitive adhesive composition comprising the partial polymerizate of the monomer mixture can be easily obtained, for example, by partially polymerizing a monomer mixture containing all of the raw material monomers by an appropriate polymerization method (for example, photopolymerization method). Other components (for example, a photopolymerization initiator, a polyfunctional monomer, a crosslinking agent, and an acrylic oligomer described later) may be added to the pressure-sensitive adhesive composition containing the partial polymer, if necessary. The method of blending such other components is not particularly limited, and may be contained in the monomer mixture in advance, or may be added to the partial polymer.

In addition, the pressure-sensitive adhesive composition disclosed in this specification may be a form in which a complete polymerisate of a monomer mixture containing monomers of some kind among monomer components (raw material monomers) is dissolved in the remaining kinds of monomers or partial polymerizates thereof. The pressure-sensitive adhesive composition of this type is also included in the examples of the pressure-sensitive adhesive composition comprising the polymer component of the monomer component and the unpolymerized compound. In the present specification, the term &quot; complete polymer &quot; means that the polymerization conversion rate exceeds 95% by weight.

As such a curing method (polymerization method) in forming a pressure-sensitive adhesive from a pressure-sensitive adhesive composition comprising a polymerizable monomer component and an unpolymerized compound, a photopolymerization method can be preferably employed. In the pressure-sensitive adhesive composition comprising the polymerization reaction product prepared by the photopolymerization method, it is particularly preferable to adopt a photopolymerization method as the curing method. Since the polymerization reaction product obtained by the photopolymerization method already contains a photopolymerization initiator, the photopolymerization initiator can be cured without adding a new photopolymerization initiator when the pressure-sensitive adhesive composition containing the polymerization reaction product is further cured. Alternatively, the pressure-sensitive adhesive composition may have a composition in which a photopolymerization initiator is added to the polymerization reaction product prepared by the photopolymerization method, if necessary. The photopolymerization initiator to be added may be the same as or different from the photopolymerization initiator used for preparing the polymerization reaction product. The pressure-sensitive adhesive composition prepared by a method other than photopolymerization can be made photocurable by adding a photopolymerization initiator. The photo-curable pressure-sensitive adhesive composition has an advantage that it can be easily formed even with a thick pressure-sensitive adhesive layer. In a preferred form, the photo-polymerization at the time of forming the pressure-sensitive adhesive from the pressure-sensitive adhesive composition can be performed by ultraviolet irradiation. For ultraviolet irradiation, known high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and the like can be used.

(A pressure-sensitive adhesive composition comprising a monomer component in the form of a complete polymer)

The pressure-sensitive adhesive composition according to another preferred embodiment includes the monomer components of the various compositions in the form of a complete polymer. Such a pressure-sensitive adhesive composition may, for example, be a solvent-type pressure-sensitive adhesive composition containing a (meth) acryl-based polymer as a complete polymeric component of a monomer component in an organic solvent, an aqueous dispersion type pressure-sensitive adhesive composition in which the (meth) acrylic polymer is dispersed in an aqueous solvent Lt; / RTI &gt;

(Crosslinking agent)

The pressure-sensitive adhesive composition disclosed in this specification may contain a crosslinking agent. As the cross-linking agent, a known or common cross-linking agent may be used in the field of the pressure-sensitive adhesive. Examples of the crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents and metal chelating crosslinking agents. These may be used singly or in combination of two or more.

The content of the crosslinking agent (the total amount thereof when two or more crosslinking agents are included) is not particularly limited. From the viewpoint of realizing a pressure-sensitive adhesive exhibiting good adhesion properties such as adhesion and cohesive force, the content of the crosslinking agent is suitably in the range of usually about 5 parts by weight or less based on 100 parts by weight of the monomer component contained in the pressure- More preferably 0.001 to 5 parts by weight, still more preferably 0.001 to 4 parts by weight, and still more preferably 0.001 to 3 parts by weight. Alternatively, it may be a pressure-sensitive adhesive composition which does not contain a crosslinking agent as described above.

((Meth) acrylic oligomer)

The pressure-sensitive adhesive composition disclosed in this specification may contain a (meth) acryl-based oligomer from the viewpoint of improvement in adhesion and the like. (Meth) acrylic oligomer has a Tg higher than the Tg of the copolymer corresponding to the composition of the monomer component (typically, it corresponds to the Tg of the (meth) acryl-based polymer contained in the pressure-sensitive adhesive formed of the pressure- It is preferable to use a polymer. By containing the (meth) acrylic oligomer, the adhesive force of the pressure-sensitive adhesive can be improved.

The (meth) acrylic oligomer preferably has a Tg of about 0 캜 to about 300 캜, preferably about 20 캜 to about 300 캜, more preferably about 40 캜 to about 300 캜. When the Tg is within the above range, the adhesive strength can be preferably improved. The Tg of the (meth) acrylic oligomer is a value calculated on the basis of the Fox equation, in the same manner as the Tg of the copolymer corresponding to the composition of the monomer component.

The weight average molecular weight (Mw) of the (meth) acrylic oligomer may typically be from about 1000 to less than about 30000, preferably from about 1500 to less than about 20,000, more preferably from about 2000 to less than about 10,000. When the Mw is within the above range, good adhesion and holding properties can be obtained. The Mw of the (meth) acrylic oligomer can be measured by gel permeation chromatography (GPC) and can be determined as a value in terms of standard polystyrene. Specifically, the measurement was carried out under the conditions of a flow rate of about 0.5 ml / min using a tetrahydrofuran solvent, using two columns of TSKgelGMH-H (20) as a column on HPLC8020 manufactured by Tosoh Corporation.

Examples of the monomer constituting the (meth) acrylic oligomer include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl Alkyl (meth) acrylates such as isodecyl (meth) acrylate, undecyl (meth) acrylate and dodecyl (meth) acrylate; Esters of (meth) acrylic acid and alicyclic alcohols such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; (Meth) acrylates obtained from terpene compound derivative alcohols; And the like. These (meth) acrylates may be used singly or in combination of two or more kinds.

Examples of the (meth) acrylic oligomer include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; Esters of (meth) acrylic acid and alicyclic alcohols such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; (Meth) acrylate having a cyclic structure such as aryl (meth) acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate as an acrylic monomer having a relatively bulky structure From the viewpoint of further improving the adhesiveness of the pressure-sensitive adhesive layer. When ultraviolet rays are employed in the synthesis of the (meth) acrylic oligomer or in the production of the pressure-sensitive adhesive layer, it is preferable to have a saturated bond in view of preventing polymerization inhibition. The alkyl (meth) Acrylate or an ester of an alicyclic alcohol can be preferably used as a monomer constituting the (meth) acrylic oligomer.

For this reason, preferred examples of the (meth) acrylic oligomer include dicyclopentyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBMA), dicyclopentanyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA), in addition to the respective homopolymers of CHMA and isobutyl methacrylate Copolymers of CHMA and IBXMA, copolymers of CHMA and acryloylmorpholine (ACMO), copolymers of CHMA and diethyl acrylamide (DEAA), copolymers of ADA and methyl methacrylate (MMA) A copolymer of DCPMA and IBXMA, a copolymer of DCPMA and MMA, and the like.

When the (meth) acrylic oligomer is contained in the pressure-sensitive adhesive composition disclosed in this specification, the content thereof is not particularly limited. The content of the (meth) acryl-based oligomer is usually about 20 parts by weight or less based on 100 parts by weight of the monomer component contained in the pressure-sensitive adhesive composition, from the viewpoint of facilitating the realization of the pressure- More preferably about 15 parts by weight or less, and more preferably about 10 parts by weight or less. The techniques disclosed in the present specification can be preferably implemented also in the form of not using a (meth) acrylic oligomer.

In addition, the pressure-sensitive adhesive composition disclosed in this specification may contain various additives known in the field of pressure-sensitive adhesives, if necessary. For example, a coloring agent such as a dye or a pigment, an antistatic agent, a surfactant, a plasticizer, a tackifier resin, a surface lubricant, a leveling agent, a softener, an antioxidant, an antioxidant, a light stabilizer, A metal powder, a granular material, a thin-walled material, and the like can be suitably added depending on the application.

As the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer in the art disclosed in this specification, an active energy ray-curable pressure-sensitive adhesive composition (typically, a photo-curable pressure-sensitive adhesive composition) can be preferably used. It is preferable that the active energy ray-curable pressure-sensitive adhesive composition contains substantially no organic solvent in view of environmental hygiene and the like. For example, a pressure-sensitive adhesive composition in which the content of the organic solvent is about 5% by weight or less (more preferably about 3% by weight or less, for example, about 0.5% by weight or less) is preferable. Further, from the viewpoint of being suitable for forming a pressure-sensitive adhesive layer in a form in which the liquid film of the pressure-sensitive adhesive composition is cured between the peeling surfaces of the pair of release films as described later, the solvent (meaning including an organic solvent and an aqueous solvent) A pressure-sensitive adhesive composition that is substantially free from the above is preferred. For example, a pressure-sensitive adhesive composition in which the content of the solvent is about 5% by weight or less (more preferably about 3% by weight or less, for example, about 0.5% by weight or less) is preferable. Here, the solvent refers to a volatile component to be removed in the process of forming the pressure-sensitive adhesive layer, that is, a volatile component that is not intended to be a constituent component of the finally formed pressure-sensitive adhesive layer.

&Lt; Production method of adhesive sheet >

The method for producing the pressure-sensitive adhesive sheet disclosed in this specification is not particularly limited. For example, any one of the pressure-sensitive adhesive compositions disclosed in this specification may be coated on the release surface of the release film and dried or cured to form a pressure-sensitive adhesive layer, thereby obtaining an inorganic material double-sided pressure-sensitive adhesive sheet containing the pressure-sensitive adhesive layer. Further, by adhering (transferring) the pressure-sensitive adhesive layer formed on the release film to the non-releasable surface of the supporting substrate in this way, the one side surface pressure-sensitive adhesive sheet with the substrate can be obtained. As another method for producing a single-sided pressure-sensitive adhesive sheet having a base, there can be mentioned a method of directly applying a pressure-sensitive adhesive composition on a non-rebated surface of a supporting base material, followed by drying or curing. The double-sided pressure-sensitive adhesive sheet having a base can be produced by a method of transferring a pressure-sensitive adhesive layer formed on a release film to a supporting substrate, a method of directly applying a pressure-sensitive adhesive composition onto a supporting substrate, followed by drying or curing, or a combination thereof.

As a method of applying the pressure-sensitive adhesive composition, various conventionally known methods can be used. Specifically, there may be mentioned, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, And an extrusion coating method by means of an extrusion coating method.

The pressure-sensitive adhesive sheet disclosed in the present specification preferably comprises a step of drying or curing a liquid film of the pressure-sensitive adhesive composition on the release face of the release film to form a pressure-sensitive adhesive layer in which the face hardened on the release face is a first pressure- Can be manufactured. According to this method, the pressure-sensitive adhesive composition (liquid film) having fluidity is brought into contact with the release surface and dried or cured, whereby the smoothness of the surface of the pressure-sensitive adhesive layer formed in contact with the release surface can be controlled with high accuracy. For example, by using a release film having a release surface with an appropriate smoothness, it is possible to stably (reproducibly improve) the first adhesive surface having a desired smoothness.

The pressure-sensitive adhesive sheet disclosed in this specification can be preferably manufactured by a method including a step of curing a liquid film of the pressure-sensitive adhesive composition between the peeling surfaces of a pair of release films to form a pressure-sensitive adhesive layer. This method is preferable as a method for producing an inorganic material double-sided pressure-sensitive adhesive sheet in which the 10-point average roughness of the first adhesive surface and the 10-point average roughness of the second adhesive surface are all within the preferred ranges disclosed in this specification. The inorganic material double-faced pressure-sensitive adhesive sheet thus obtained can be preferably applied to the production of a single-sided pressure-sensitive adhesive sheet having a substrate or a double-faced pressure-sensitive adhesive sheet having a substrate by bonding the thus obtained inorganic material pressure- As a method for disposing a liquid film of a pressure-sensitive adhesive composition between the peeling surfaces of a pair of peeling films, there is a method in which a liquid pressure-sensitive adhesive composition is applied to the peeling surface of the first peeling film and then a second peeling film is applied to the liquid film of the pressure- Method can be adopted. Alternatively, the first peeling film and the second peeling film may be peeled from each other so as to face each other and be supplied between the pair of rolls, and a liquid adhesive composition may be supplied between the peeling surfaces. The application of the pressure-sensitive adhesive composition is preferably performed at 80 DEG C or lower, more preferably at 60 DEG C or lower (for example, 40 DEG C or lower). This suppresses the roughening of the pressure-sensitive adhesive layer due to the difference in thermal expansion coefficient between the release film and the pressure-sensitive adhesive layer, so that the pressure-sensitive adhesive surface with higher smoothness can be formed.

The gel fraction of the pressure-sensitive adhesive layer disclosed in this specification is not particularly limited, but is preferably about 99.5% by weight or less, more preferably about 20 to 99.5% by weight, still more preferably about 50 to 99.5% by weight Do. When the pressure-sensitive adhesive composition contains a crosslinking agent, it is possible to control the gel fraction by adjusting the addition amount of the crosslinking agent and taking into account the effect of the crosslinking treatment temperature and the crosslinking treatment time.

Although not particularly limited, the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet disclosed in this specification preferably has a haze value of 2% or less at a thickness of 50 m. In the pressure-sensitive adhesive layer used for optical use, it is particularly significant that the haze value is 2% or less. The haze value of the pressure-sensitive adhesive layer is preferably 0 to 1.5%, more preferably 0 to 1%. The haze value can be measured by attaching a pressure-sensitive adhesive layer formed so as to have a thickness of about 50 mu m to one side of an alkali glass plate and using a haze meter. As the haze meter, MR-100 manufactured by Murakami Shikisai Gijutsu Kenkyo Co., Ltd. or its equivalent can be used. In the measurement, an alkali glass plate to which a pressure-sensitive adhesive layer is adhered is arranged such that the pressure-sensitive adhesive layer is on the light source side. When the alkali glass itself has a haze value, a value obtained by subtracting the haze value from the alkali glass plate itself from the measured value is regarded as the haze value of the pressure-sensitive adhesive layer.

<Peeling film>

The release film in the techniques disclosed in this specification is not particularly limited and can be appropriately selected according to the purpose. Non-limiting examples of the release film that can be used include a release film having a release treatment layer on one or both surfaces of the release film base and the surface of the release treatment layer being peeled off; And a release film comprising a fluorine-based polymer (such as polytetrafluoroethylene) or a low-adhesion resin of a polyolefin-based resin (such as polyethylene or polypropylene). As the release film substrate, a plastic film, paper (resin impregnated or resin laminated paper), or the like can be used. The peeling treatment layer may be formed by surface-treating the peeling film base with a peeling treatment agent. Examples of the peeling agent include a silicone peeling agent, a long chain alkyl peeling agent, a fluorine peeling agent, molybdenum sulfide (IV), and the like. In one aspect, a release film having a release treatment layer by a silicone-based release agent can be preferably employed.

As the release film disclosed in this specification, those having a release treatment layer on the surface of a plastic film as a release film base can be preferably employed. The material constituting such a plastic film may be arbitrarily selected from the same materials as those exemplified as the plastic film used for the supporting substrate. From the viewpoint of dimensional stability and strength, a plastic film containing a polyester-based resin film (typically, a polyethylene terephthalate film) can be preferably employed. A plastic film having transparency in at least a part of the region is preferable.

In the techniques disclosed in this specification, the plastic film used as the above-mentioned support substrate or release film substrate may be any of an unstretched film, a uniaxially stretched film, and a biaxially stretched film. The plastic film may have a single-layer structure or a multi-layer structure including two or more sub-layers. The plastic film may be used for a supporting substrate or a release film base of an adhesive sheet such as an antioxidant, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a coloring agent such as a pigment or a dye, a lubricant, a filler, an antistatic agent, Known additives may be blended. In the multilayered plastic film, each additive may be incorporated in all of the sublayers, or may be incorporated in only some of the sublayers.

As the release film in the technology disclosed in this specification, a release film having a release treatment layer on the surface of a plastic film (release film base material) and containing no particles or containing particles having a diameter of 5 탆 or less is preferably used Can be adopted. Particles (particularly, inorganic particles) having a diameter of more than 5 占 퐉 contained in the release film may lower the smoothness of the release surface in the free state of the release film. Further, even if the peelable film containing particles having a diameter exceeding 5 占 퐉 has a high smoothness in a free state, the particles are protruded from the peelable film by bending deformation, stretching deformation, compression in the thickness direction The smoothness of the release surface is lowered, and further, the smoothness of the adhesive surface in contact with the release surface may be lowered. In one form, a release film that does not substantially contain particles having a diameter exceeding 5 占 퐉, that is, a release film that does not contain particles having a diameter exceeding 5 占 퐉 may be used, except for the incorporation of unintentional foreign matter.

Further, the particles having a diameter of more than 5 占 퐉 may be inorganic particles that can be blended in the release film base for the purpose of, for example, lubricant, pigment, filler and the like. Non-limiting examples of such inorganic particles include silica, alumina, kaolin, talc, mica, calcium carbonate and the like.

The thickness of the release film is not particularly limited. From the balance between the strength and the flexibility, a release film having a thickness of about 10 μm to about 500 μm can be preferably employed. The smoothness of the adhesive surface due to the external force beyond the peeling film (for example, the smoothness degradation due to the pressing of the foreign matter mixed with the peeling film onto the adhesive surface when the pressure sensitive adhesive sheet with the peeling film is wound in a roll form) It is preferable that the thickness of the release film is usually about 20 mu m or more and more preferably about 25 mu m or more (for example, about 30 mu m or more). The thickness of the release film is usually about 250 占 퐉 or less, preferably about 125 占 퐉 or less (for example, about 50 占 퐉 or less, for example, Preferably about 100 mu m or less), and more preferably about 80 mu m or less. In one form, a release film having a thickness of about 75 占 퐉 or less (for example, about 50 占 퐉 or less) can be preferably used.

In the pressure-sensitive adhesive sheet having a release film disclosed in this specification, the 10-point average roughness (Rz _R1 ) of the release face of the first release film abutting the first pressure-sensitive adhesive sheet may be, for example, about 2000 nm or less. From the viewpoint of suppressing the decrease in the smoothness of the first adhesive surface during storage of the release sheet with a release film, Rz _R1 is suitably about 1500 nm or less, preferably about 1000 nm or less, more preferably about 500 nm or less , And more preferably about 300 nm or less (for example, about 250 nm or less). When the first adhesive surface is the surface of the pressure-sensitive adhesive layer formed of a liquid pressure-sensitive adhesive composition on the release surface of the first release film, the first release film preferably has Rz _R1 of about 1200 nm or less (typically about 700 nm or less Preferably about 500 nm or less, more preferably about 400 nm or less, for example, about 300 nm or less). The lower limit of Rz _R1 is not particularly limited. From the viewpoints of easiness in production and handleability of the first release film, a first release film having Rz _R1 of about 50 nm or more (for example, about 100 nm or more) can be preferably used in one form.

In the case where the release sheet-adhered sheet disclosed in this specification is in the form of a double-sided pressure-sensitive adhesive sheet having a release film comprising a double-sided pressure-sensitive adhesive sheet, a first release film and a second release film, The 10-point average roughness (Rz _R2 ) of the release face of the second release film is not particularly limited and may be, for example, about 3000 nm or more. In one aspect, a second release film having Rz _R2 less than about 3000 nm (preferably less than about 2000 nm) can be preferably employed. In the case where the 10-point average roughness Rz _A2 of the second pressure-sensitive adhesive surface is 1000 nm or less, Rz _R2 is about 2,000 nm or less (typically about 1,500 nm or less, preferably about 1,500 nm or less, About 1000 nm or less, more preferably about 500 nm or less, and more preferably about 300 nm or less, for example, about 250 nm or less). When the second adhesive surface is the surface of the pressure-sensitive adhesive layer formed of a liquid pressure-sensitive adhesive composition on the release surface of the second release film, the second release film preferably has Rz _R2 of about 1200 nm or less (typically about 700 nm or less Preferably about 500 nm or less, more preferably about 400 nm or less, for example, about 300 nm or less). The lower limit of RZR2 is not particularly limited. In one aspect, a second peelable film having Rz _R2 of greater than or equal to about 50 nm (e.g., greater than or equal to about 100 nm) may be preferably used.

In the technique disclosed in this specification, it is preferable that the release surface of the release film constituting the release sheet-equipped pressure-sensitive adhesive sheet has a smoothness approximate to the smoothness of the adhesive surface to which the release surface abuts. As a result, the change in the smoothness of the adhesive surface during storage of the release sheet having the release film is more restrained, and the performance stability of the adhesive sheet tends to be improved. In the pressure-sensitive adhesive sheet having a release film according to one aspect of the invention, the difference between the ten points average roughness of the first adhesive surface and the first release surface in contact therewith, that is, | Rz _R1 -Rz _A1 | is about 300 nm or less 250 nm or less), preferably about 150 nm or less, and more preferably about 100 nm or less. From the viewpoint of the performance stability of the adhesive sheet, it is preferable that the 10-point average roughness of the first adhesive surface is smaller than the 10-point average roughness of the first release surface. That is, Rz _A1 <Rz _R1 is is desired, the | Rz _R1 -Rz _A1 | of the value _A1 and Rz _<R1 Rz of at least one release film having a pressure-sensitive adhesive sheet satisfying the (preferably both) is, for example, And drying or curing the liquid film of the pressure-sensitive adhesive composition on the release face of the first release film constituting the pressure-sensitive adhesive sheet having the release film.

In the case where the pressure-sensitive adhesive sheet having a release film disclosed in this specification is in the form of a double-sided pressure-sensitive adhesive sheet having a release film comprising a pressure-sensitive adhesive double coated sheet, a first release film and a second release film, Rz _R2 -Rz _A2 | can be about 300 nm or less (for example, about 250 nm or less), preferably about 150 nm or less, or about 100 nm or less Is more preferable. From the viewpoint of the performance stability of the pressure-sensitive adhesive sheet, it is preferable that the 10-point average roughness of the second adhesive surface is smaller than the 10-point average roughness of the second release surface. That is, it is preferable that Rz _A2 < Rz _R2 . The pressure-sensitive adhesive sheet having a release film satisfying the value of | Rz _R2 -Rz _A2 | and at least one of (preferably both) of Rz _A2 <Rz _R2 can be obtained by, for example, And a step of curing the liquid film of the pressure-sensitive adhesive composition between the release face of the second release film and the release face of the second release film.

The smoothness of the back surface (that is, the surface opposite to the release surface) of the release film constituting the pressure-sensitive adhesive sheet having a release film is not particularly limited. And the peelable film-coated pressure-sensitive adhesive sheet which can be rolled in a rolled form, the 10-point average roughness of the back surface of the release film is preferably set to about 1 mm or less from the viewpoint of preventing the smoothness of the adhesive surface caused by the unevenness of the back surface in the above- (Preferably about 4000 nm or less, for example, about 3000 nm or less).

The peeling film on the first adhesive surface may be peeled off from the peeling film on the adherend until the adhesive sheet is adhered to the adherend (this may be the adhesive sheet included in the peeling film- It can be preferably used in the form of being exchanged with a film. Hereinafter, the exfoliated film to be exchanged is also referred to as &quot; exchange film &quot;. The 10-point average roughness (Rz _E1 ) of the first peeling surface of the exchange film (i.e., the peeling surface disposed in contact with the first adhesive surface) is not particularly limited and may be, for example, about 50 nm or more (typically about 100 nm or more) . In one form, an exchange film can preferably be employed in which Rz _E1 is greater than about 250 nm (more preferably greater than about 500 nm, such as greater than about 700 nm). The pressure-sensitive adhesive sheet disclosed in this specification can suppress the deterioration of the smoothness of the first adhesive surface even in the case of using the exchange film in which Rz _E1 is about 1000 nm or more (and moreover, about 1200 nm or more, for example, about 1500 nm or more) The effect can be significantly exhibited. The upper limit of Rz _E1 is not particularly limited. Normally, an exchange film having a Rz _E1 of about 3000 nm or less (typically about 2000 nm or less) can be preferably used. In one form, Rz _E1 of the exchange film may be about 1500 nm or less, or about 1000 nm or less. As the exchange film, those having the same constitution (material, thickness, surface roughness, etc.) as those of the release film before exchange may be used, or those having different constitutions may be used.

In one preferred form, it is possible to employ a film having a larger value of Rz _E1 than the 10-point average roughness (Rz _R1 ) of the first peeled surface of the release film before exchange (which may be the original release film) have. In one form, an exchange film with Rz _E1 / Rz _R1 of at least about 2 (preferably at least about 3) may be used. The pressure-sensitive adhesive sheet disclosed in this specification can also be used in a use mode in which, for example, an exchange film in which Rz _E1 / Rz _R1 is about 5 or more (more preferably about 7 or more) is used, The effect can be significantly exhibited. The upper limit of Rz _E1 / Rz _R1 is not particularly limited, but usually about 20 or less (typically about 15 or less, for example, about 10 or less) is suitable.

<Applications>

The pressure-sensitive adhesive layer or the pressure-sensitive adhesive sheet disclosed in this specification is preferable for optical use because it has a high smoothness of the pressure-sensitive adhesive surface and is difficult to damage the smoothness of the pressure-sensitive adhesive surface. For example, it is useful as an adhesive optical member using an optical member as the supporting substrate. Such a sticky optical member can also be recognized as a single-sided pressure-sensitive adhesive sheet having a substrate having an optical member as a supporting substrate on the first adhesive surface or the second adhesive surface of any one of the double-sided adhesive sheets disclosed in this specification. And a shape having an optical member on the second adhesive surface. In this form, a sticking-type optical member having a release film having a release film on the first adhesive surface may be constituted.

When an optical film is used as the optical member, the adhesive optical member is used as an optical film having a pressure-sensitive adhesive layer. Examples of the optical film include a polarizing plate, a retardation plate, an optical compensation film, a brightness enhancement film, a hard coating (HC) film, an antireflection film, an impact absorption film, an antifouling film, a photochromic film, A conversion film, or a laminate thereof may be used. The pressure-sensitive adhesive layer or pressure-sensitive adhesive sheet disclosed in this specification is also preferable for use in the field of ophthalmology. Further, the pressure-sensitive adhesive layer or the pressure-sensitive adhesive sheet of the present invention is not limited to the optical and ophthalmic uses as described above. For example, in the form of a pressure-sensitive adhesive sheet using a general antifouling film, a heat insulating film, It can be applied to applications.

The matters disclosed by this specification include the following.

(1) A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer,

Wherein the pressure-sensitive adhesive sheet has a first surface and a second surface,

Wherein the first surface is a first adhesive surface constituted by one surface of the pressure-sensitive adhesive layer,

Point average roughness (Rz _A1 ) of the first adhesive surface is about 1000 nm or less,

Wherein the pressure-sensitive adhesive layer has a storage elastic modulus (G ' ₁₀₀ ) at 100 ° C of about 0.08 MPa or more.

(2) The pressure-sensitive adhesive sheet according to (1), wherein the pressure-sensitive adhesive layer has a storage elastic modulus at 100 ° C (G ' ₁₀₀ ) to a storage elastic modulus at 23 ° C (G' ₂₃ ) of about 35% or more.

(3) The pressure-sensitive adhesive layer, 23 ℃ storage modulus (G _'23) is approximately less than 0.30MPa, the pressure-sensitive adhesive sheet according to (1) or (2).

(4) The pressure-sensitive adhesive sheet according to any one of (1) to (3), wherein the second surface is a double-sided pressure-sensitive adhesive sheet as a second pressure-sensitive adhesive surface.

(5) The pressure-sensitive adhesive sheet according to (4), wherein the ten-point average roughness (Rz _A2 ) of the second adhesive surface is about 2000 nm or less (for example, about 1000 nm or less).

(6) The pressure-sensitive adhesive sheet according to (4) or (5), wherein the second adhesive surface is constituted by the other surface of the pressure-sensitive adhesive layer.

(7) The method according to any one of (4) to (6) above, wherein one of the 10-point average roughness (Rz _A1 ) of the first adhesive surface and the 10-point average roughness (Rz _A2 ) Sensitive adhesive sheet.

(8) The method according to any one of (4) to (7) above, wherein the ten-point average roughness (Rz _A1 ) of the first adhesive surface and the ten-point average roughness (Rz _A2 ) Adhesive sheet.

9, the first adhesive 10-point average roughness of the surface (Rz _A1) and 10-point average roughness of the second adhesive surface (Rz _A2) of the difference (| Rz -Rz _{A1 A2} |) is less than or equal to about 250nm, the ( Sensitive adhesive sheet according to any one of (4) to (8).

(10) The pressure-sensitive adhesive sheet according to any one of (1) to (9), wherein the pressure-sensitive adhesive sheet is an inorganic material double-sided pressure-sensitive adhesive sheet comprising a single-layer pressure-sensitive adhesive layer.

(11) The pressure-sensitive adhesive sheet according to any one of (1) to (10), wherein the pressure-sensitive adhesive layer contains a (meth) acryl-based polymer in a proportion exceeding 50% by weight of the polymer component contained in the pressure-sensitive adhesive layer.

(12) The (meth) acrylic polymer is a monomer component constituting the (meth) acryl-based polymer, and the following component (A)

Alkyl (meth) acrylates having an alkyl group of 2 to 18 carbon atoms at the terminal of the ester;

Sensitive adhesive sheet according to the above (11).

(13) The pressure-sensitive adhesive sheet according to the above (11) or (12), wherein the proportion of the component (A) in the entire monomer component is about 30 wt% to about 70 wt%.

(14) The (meth) acrylic polymer is a monomer component constituting the (meth) acryl-based polymer, and the following component (B)

Alicyclic monomers;

Sensitive adhesive sheet according to any one of (11) to (13) above.

(15) The component (B) is at least one member selected from the group consisting of cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl The pressure-sensitive adhesive sheet according to any one of (11) to (14), wherein the pressure-sensitive adhesive sheet is at least one selected from the group consisting of cyclooctyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate.

(16) The pressure-sensitive adhesive sheet according to any one of (11) to (15), wherein the ratio of the component (B) in the entire monomer component is about 20 wt% to about 50 wt%.

(17) The above-mentioned (meth) acrylic polymer is a monomer component constituting the (meth) acryl-based polymer, and the following component (C)

A monomer having at least one of a hydroxyl group and a carboxyl group;

The pressure-sensitive adhesive sheet according to any one of (11) to (16) above, further comprising:

(18) The pressure-sensitive adhesive sheet according to any one of (11) to (17), wherein the proportion of the component (C) in the entire monomer component is about 15 wt% to about 30 wt%.

(19) The (meth) acryl-based polymer further comprises a polyfunctional monomer as a monomer component constituting the (meth) acryl-based polymer,

The pressure-sensitive adhesive sheet according to any one of (11) to (18), wherein the proportion of the polyfunctional monomer in the entire monomer component is about 3% by weight or less.

(20) The pressure-sensitive adhesive sheet according to any one of (11) to (19), wherein the (meth) acryl-based polymer is an ultraviolet polymer of the monomer component.

(21) A method for producing a pressure-sensitive adhesive sheet according to any one of (11) to (20)

And forming the pressure-sensitive adhesive layer using a pressure-sensitive adhesive composition comprising at least a part of the monomer component in the form of a polymer.

(22) The pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition to the release face of the release film, and drying or curing the pressure-sensitive adhesive composition on the release face. .

(23) The method for producing a pressure-sensitive adhesive sheet according to (21) or (22), wherein the pressure-sensitive adhesive composition has an organic solvent content of about 5% by weight or less.

(24) The method of producing a pressure sensitive adhesive layer according to any one of (21) to (23), wherein the pressure sensitive adhesive layer is formed by curing a liquid film of the pressure sensitive adhesive composition between the peeling surfaces of a pair of release films A method for producing a pressure-sensitive adhesive sheet according to claim 1.

(25) A pressure-sensitive adhesive sheet according to any one of (1) to (20)

A first peeling film disposed on the first adhesive surface,

Sensitive adhesive sheet having a release film.

(26) A pressure-sensitive adhesive sheet according to any one of (4) to (20)

A first peeling film disposed on the first adhesive surface,

And a second peeling film disposed on the second adhesive surface

Sensitive adhesive sheet having a release film.

27 in which the first release film difference within about 250nm of the first 10-point average roughness of the delaminated surface in contact with the adhesive surface (Rz _R1) with the first adhesive 10-point average roughness of the surface (Rz _A1), wherein Sensitive adhesive sheet having a release film according to (25) or (26).

(28) The pressure-sensitive adhesive sheet having a peelable film according to (26) or (27), wherein Rz _A1 <Rz _R1 and Rz _A2 <Rz _R2 satisfy.

(29) The method according to any one of (25) to (28), wherein the first release film comprises at least one inorganic particle selected from the group consisting of silica, alumina, kaolin, talc, mica, and calcium carbonate. Sensitive adhesive sheet having a release film.

(30) The method of manufacturing a semiconductor device according to any one of (25) to (25), wherein the thickness of the first peeling film is about 10 탆 or more and about 500 탆 or less (preferably about 20 탆 or more and about 100 탆 or less, more preferably about 25 탆 or more and about 80 탆 or less) Sensitive adhesive sheet according to any one of (1) to (29).

(31) A pressure-sensitive adhesive sheet according to any one of (4) to (20)

And an optical member disposed on the second adhesive surface of the pressure-

And an adhesive layer.

(32) A method for preparing a pressure-sensitive adhesive sheet having a release film according to any one of (26) to (30)

Peeling the first peelable film from the first adhesive surface and bonding the peeled surface of another peelable film to the exposed first adhesive surface; And

Attaching the second adhesive surface to the article as the adherend;

Wherein the pressure-sensitive adhesive sheet-containing article is a sheet.

(33) The other release film, wherein the first peelable film has a ten-point average roughness Rz (Rz _R1 ) of the peeled surface of the other peelable film, _(E1 ) is larger than that of the pressure-sensitive adhesive sheet.

Example

Hereinafter, some embodiments according to the present invention will be described, but the present invention is not intended to be limited to those shown in these embodiments.

&Lt; Preparation of pressure-sensitive adhesive composition &

(Pressure-sensitive adhesive composition C1)

40 parts by weight of n-butyl acrylate, 41 parts by weight of cyclohexyl acrylate, 19 parts by weight of 4-hydroxybutyl acrylate, and 2,2-dimethoxy-1,2-diphenylethane- 0.05 part by weight of 1-on (trade name: Irgacure 651, manufactured by BASF) and 0.05 part by weight of 1-hydroxycyclohexyl-phenyl-ketone (trade name: Irgacure 184, (Monomer syrup) was prepared by irradiating ultraviolet rays under a nitrogen atmosphere. To the obtained monomer syrup, 0.1 part by weight of 1,6-hexanediol diacrylate was added and uniformly mixed to prepare a pressure-sensitive adhesive composition C1.

(Pressure-sensitive adhesive compositions C2 to C4)

In the preparation of the pressure-sensitive adhesive composition C1, the amount of 1,6-hexanediol diacrylate added was changed to 0.3 part by weight in the pressure-sensitive adhesive composition C2, 0.05 part by weight in the pressure-sensitive adhesive composition C3, and 0 part by weight in the pressure- As for the other points, the pressure-sensitive adhesive compositions C2 to C4 were prepared in the same manner as the preparation of the pressure-sensitive adhesive composition C1.

In addition, these pressure-sensitive adhesive compositions C1 to C4 are all compositions in a no-solvent form. Specifically, the content of the solvent in all of the pressure-sensitive adhesive compositions C1 to C4 is less than 5% by weight, more specifically less than 1% by weight.

<Production of pressure-sensitive adhesive sheet>

A release film R1 having a release treatment layer of a silicone type release agent A1 on one side of a 38 占 퐉 -thick polyethylene terephthalate (PET) film F1 and having a ten-point average roughness of 211 nm on the release side (the surface of the release treatment layer) A release film R2 having a release treatment layer of silicone-based release agent A1 on one side of a 38 占 퐉 -thick PET film F2 and having a 10-point average roughness of 1610 nm on the release side and a release film R2 having a 10- A release film R 3 having a release treatment layer and a 10-point average roughness of the release surface of 1,610 nm was prepared. The release surface of the release film R 3 is formed so that the release strength from the pressure-sensitive adhesive layer is higher than the release surface of the release films R 1 and R 2. Using this release film, a pressure-sensitive adhesive sheet was produced as follows.

The 10-point average roughness of each of the peeling films of the peeling films R1, R2, and R3 was measured with a drop of water dropwise on a slide glass S1112No.2 (manufactured by Matsunami Glass Co., Ltd.) Is a measurement value obtained in the same manner as the surface smoothness measurement of the first adhesive surface described later except for the back surface (the surface which is not peeled) is disposed in close contact with the slide glass.

(Example 1)

The pressure-sensitive adhesive composition C1 prepared above was coated on the release face of the release film R1 to form a liquid film of the pressure-sensitive adhesive composition on the release face. The application amount of the pressure-sensitive adhesive composition was adjusted so that the thickness of the pressure-sensitive adhesive layer finally formed was 50 占 퐉. Subsequently, a release film R3 was placed on the liquid film so that the release face of the release film R3 was in contact with the liquid film. Whereby the liquid film was blocked from oxygen. Using a chemical light lamp (manufactured by Toshiba Corporation), both surfaces (the first surface and the second surface) of the liquid film of the pressure-sensitive adhesive composition C1 were in contact with the peeling films of the peeling films R1 and R3, Curing the liquid film to form a pressure-sensitive adhesive layer to obtain the pressure-sensitive adhesive sheet S1 of Example 1 containing the pressure-sensitive adhesive layer (that is, the ultraviolet cured product of the liquid film). The pressure-sensitive adhesive sheet S1 is a pressure-sensitive adhesive sheet having a release film-provided pressure-sensitive adhesive sheet in which the release faces of the release films R1 and R3 used for manufacturing the pressure-sensitive adhesive sheet S1 abut against the first face (first pressure-sensitive adhesive face) and the second face Respectively.

The value of the roughness is a value measured by an industrial UV checker (trade name "UVR-T1" manufactured by Topcon Co., Ltd., light receiving part type UD-T36) having a peak sensitivity wavelength of about 350 nm.

(Examples 2 and 3)

Sensitive adhesive sheets S2 and S3 relating to Examples 2 and 3 were obtained in the same manner as in the production of the pressure-sensitive adhesive sheet S1 of Example 1 except that the pressure-sensitive adhesive compositions C2 and C3 were used in place of the pressure-sensitive adhesive composition C1. The pressure sensitive adhesive sheets S2 and S3 constitute a pressure sensitive adhesive sheet having a release film in which the release faces of the release films R1 and R3 used for the production of the pressure sensitive adhesive sheet abut against the first pressure sensitive adhesive face and the second pressure sensitive adhesive face, respectively.

(Comparative Example 1)

In the production of the pressure-sensitive adhesive sheet S2 according to Example 2, the release film R2 was used in place of the release film R1. That is, the pressure-sensitive adhesive composition C2 was applied on the release face of the release film R2 to form a liquid film of the pressure-sensitive adhesive composition, and the release film R3 was placed on the liquid film so that the release face of the release film was in contact with the liquid film. The pressure-sensitive adhesive sheet S4 of Comparative Example 1 was obtained in the same manner as in Example 2 except that ultraviolet rays were irradiated while both surfaces of the liquid film of the pressure-sensitive adhesive composition C2 were in contact with the peeling films of the release films R2 and R3, respectively. The pressure-sensitive adhesive sheet S4 constitutes a pressure-sensitive adhesive sheet having a release film in which the release faces of the release films R2 and R3 used for manufacturing the pressure-sensitive adhesive sheet S4 abut against the first pressure-sensitive adhesive surface and the second pressure-sensitive adhesive surface, respectively.

(Comparative Example 2)

A pressure-sensitive adhesive sheet S5 relating to Comparative Example 2 was obtained in the same manner as in the production of the pressure-sensitive adhesive sheet S1 according to Example 1 except that the pressure-sensitive adhesive composition C4 was used instead of the pressure-sensitive adhesive composition C1. The adhesive sheet S5 constitutes a release sheet provided with a release film in which the release surfaces of the release films R1 and R3 used for the production of the adhesive sheet S5 abut against the first adhesive surface and the second adhesive surface, respectively.

The pressure-sensitive adhesive sheet of each example was stored for 7 days in an environment of 23 deg. C and 50% RH in the form of the pressure-sensitive adhesive sheet with the release film after the production, and then provided for the following measurement and test.

&Lt; Measurement of storage elastic modulus &

A plurality of pressure-sensitive adhesive sheets (pressure-sensitive adhesive layers having a thickness of about 50 탆) relating to each example were superimposed to produce a pressure-sensitive adhesive layer having a thickness of about 2 mm. The pressure-sensitive adhesive layer was sandwiched between parallel plates and punched in a disc shape having a diameter of 7.9 mm. The samples were fixed and viscoelasticity was measured under the following conditions by a viscoelasticity tester (ARES, manufactured by TA Instruments) G _'23 ) and a storage elastic modulus at 100 ° C (G' ₁₀₀ ).

· Measuring mode: Shearing mode

· Temperature range: -70 ° C to 150 ° C

Heating rate: 5 ° C / min

· Measuring frequency: 1Hz

<10 point average roughness of the first adhesive surface in the original composition>

The peelable film on the second adhesive surface of the pressure-sensitive adhesive sheet relating to each example was removed under the environment of 23 ° C and 50% RH, and the exposed second adhesive surface was attached to the slide glass S1112No.2 (manufactured by Matsunami Glass Co., Ltd.) Respectively. Then, the release film on the first adhesive surface of the adhesive sheet attached to the slide glass was manually peeled in the 180 degree direction at a peeling rate of about 10 m / min, whereby the 10-point average roughness Was measured by a surface roughness measuring apparatus (Wyco NT-9100, manufactured by Veeco Co., Ltd.) of the optical interference system. The measurement was performed within 10 minutes after the release film was removed from the first adhesive surface. The measurement conditions are as follows.

· Measurement area / times: 622 μm × 467 μm

   (Objective lens: 10 times, FOV (inner lens): 1.0 times)

· Measurement mode: VSI (Vertical Scan Interferometry)

· Back Scanning: 5㎛

· Measuring distance: 10㎛

· Threshold: 0.1%

· Scan speed: 1x (Single scan)

From the data set obtained by the measurement, the highest peak in the measurement plane was taken out, and the elevation of the peak was H1. The range of 11 x 11 pixels around H1 was masked, and the highest peak outside the masked range was taken and the top of the peak was H2. This operation was repeated to specify H3 to H10. In this way, elevations (H1 to H10) from the highest mountain to the tenth mountain were obtained. In the same manner, the elevations (L1 to L10) of the valley floor from the lowest valley to the tenth valley in the measurement plane were obtained. From these values, Rz was calculated by the following formula. Where H _j is the height of each mountain top (elevation), and L _j is the depth (elevation) of each valley bottom.

The measurement was carried out five times (i.e., N = 5), and the average value thereof was obtained.

&Lt; 10 point average roughness of first adhesive surface after peeling film replacement >

(Test Example 1)

The release film R1 was manually peeled from the first adhesive surface of the pressure-sensitive adhesive sheet S1 of Example 1 at 180 deg. At a peeling speed of about 10 m / min under the environment of 23 deg. C and 50% RH. On this exposed first adhesive surface, a separate release film R1 was immediately bonded and a 2 kg roller was reciprocated one time at a moving speed of about 300 mm / min. Thus, the release film R1 for protecting the first adhesive surface of the pressure-sensitive adhesive sheet of Example 1 was replaced with another release film R1 (replaced). This was held for 2 hours in an environment of 23 ° C and 50% RH, and then the peeled release film R1 was manually peeled in a 180 ° direction at a peeling rate of about 10 m / min. The 10- Were measured in the same manner as above.

(Test Example 2)

In this test example, the release film R1 on the first adhesive surface of the pressure-sensitive adhesive sheet S2 of Example 2 was replaced with the release film R2. In other respects, in the same manner as in Test Example 1, the peeled release film R2 was removed and the 10-point average roughness of the exposed first adhesive surface was measured.

(Test Example 3)

In this test example, the release film R1 on the first adhesive surface of the pressure-sensitive adhesive sheet S3 of Example 3 was replaced with the release film R2. In other respects, in the same manner as in Test Example 1, the peel-off film R2 was peeled off and the 10-point average roughness of the exposed first adhesive surface was measured.

(Test Example 4)

In this test example, the release film R1 on the first adhesive surface of the pressure-sensitive adhesive sheet S4 of Comparative Example 1 was replaced with the release film R2. In other respects, in the same manner as in Test Example 1, the peel-off film R2 was peeled off and the 10-point average roughness of the exposed first adhesive surface was measured.

(Test Example 5)

In this test example, the release film R2 on the first adhesive surface of the pressure-sensitive adhesive sheet S4 of Comparative Example 1 was replaced with the release film R1. In other respects, in the same manner as in Test Example 1, the peeled release film R1 was peeled off and the 10-point average roughness of the exposed first adhesive surface was measured.

(Test Example 6)

In this test example, the release film R2 on the first adhesive surface of the pressure-sensitive adhesive sheet S5 of Comparative Example 2 was replaced with another release film R2. In other respects, in the same manner as in Test Example 1, the peel-off film R2 was peeled off and the 10-point average roughness of the exposed first adhesive surface was measured.

The obtained results are shown in Table 1.

As shown in Table 1, in the pressure-sensitive adhesive sheet in which the 10-point average roughness of the first pressure-sensitive adhesive surface is 1000 nm or less, the pressure-sensitive adhesive layer constituting the first pressure-sensitive adhesive surface has a storage elastic modulus at 100 ° C of 0.08 MPa or more, It was confirmed that the decrease in the smoothness of the first adhesive surface caused by the above-mentioned adhesive was remarkably suppressed. Further, in the adhesive sheet S4 having a low smoothness of the first adhesive surface in the initial construction of manufacture, even after the release film on the first adhesive surface is replaced with a higher smoothness, the improvement in smoothness of the first adhesive surface is not visible I did.

Although specific embodiments of the present invention have been described in detail, they are merely illustrative and do not limit the scope of the claims. The techniques described in the claims include various modifications and changes to the embodiments described above.

1, 2: pressure-sensitive adhesive sheet
1A: first surface (first adhesive surface)
1B: second surface (second adhesive surface)
2A: first side (first side)
2B: second side (non-adhesive side)
11: Pressure-sensitive adhesive layer
11A: One surface
11B: the other surface
15: support substrate
15A: first side
15B: second side
21: First release film
21A: Surface (first peeled surface)
21B:
22: Second release film
22A: Surface (second peeled surface)
100, and 200: a pressure-sensitive adhesive sheet having a release film

Claims (20)

A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer,
Wherein the pressure-sensitive adhesive sheet has a first surface and a second surface,
Wherein the first surface is a first adhesive surface constituted by one surface of the pressure-sensitive adhesive layer,
The 10-point average roughness of the first adhesive surface is 1000 nm or less,
Wherein the pressure-sensitive adhesive layer has a storage elastic modulus at 100 캜 of 0.08 MPa or more. The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a storage elastic modulus at 100 ° C of 35% or more with respect to a storage elastic modulus at 23 ° C. The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the pressure-sensitive adhesive layer has a storage elastic modulus at 23 캜 of less than 0.30 MPa. The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer comprises a (meth) acryl-based polymer in a proportion exceeding 50% by weight of the polymer component contained in the pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet according to claim 4, wherein the (meth) acryl-based polymer comprises an alkyl (meth) acrylate having an ester group at the terminal of an ester of an alkyl group having 2 to 18 carbon atoms as a monomer component constituting the (meth) . The pressure-sensitive adhesive sheet according to claim 5, wherein the ratio of the alkyl (meth) acrylate having the alkyl group having 2 to 18 carbon atoms at the terminal of the ester to the entire monomer component is 30% by weight or more and 70% by weight or less. The pressure-sensitive adhesive sheet according to any one of claims 4 to 6, wherein the (meth) acryl-based polymer further comprises an alicyclic monomer as a monomer component constituting the (meth) acryl-based polymer. The pressure-sensitive adhesive sheet according to any one of claims 4 to 7, wherein the proportion of the alicyclic monomers in the entire monomer component is 20% by weight or more and 50% by weight or less. The method according to any one of claims 4 to 8, wherein the (meth) acryl-based polymer further comprises a monomer having at least any one of a hydroxyl group and a carboxyl group as a monomer component constituting the (meth) Adhesive sheet. 10. The pressure-sensitive adhesive sheet according to any one of claims 4 to 9, wherein the proportion of the monomer having at least any one of the hydroxyl group and the carboxyl group in the monomer component is from 15% by weight to 30% by weight. 11. The thermoplastic resin composition according to any one of claims 4 to 10, wherein the (meth) acrylic polymer further comprises a polyfunctional monomer as a monomer component constituting the (meth) acrylic polymer,
Wherein the ratio of the polyfunctional monomer to the entire monomer component is 3% by weight or less. 12. The pressure-sensitive adhesive sheet according to any one of claims 4 to 11, wherein the (meth) acryl-based polymer is an ultraviolet polymer of the monomer component. 13. The adhesive sheet according to any one of claims 1 to 12, wherein the second surface is a second adhesive surface. The pressure-sensitive adhesive sheet according to claim 13, wherein the 10-point average roughness of the second adhesive surface is 2000 nm or less. The pressure-sensitive adhesive sheet according to claim 14, wherein the 10-point average roughness of the second adhesive surface is 1000 nm or less. The pressure-sensitive adhesive sheet according to any one of claims 13 to 15, wherein one of the 10-point average roughness of the first adhesive surface and the 10-point average roughness of the second adhesive surface is 500 nm or less. The pressure-sensitive adhesive sheet according to any one of claims 13 to 16, wherein the second adhesive surface is constituted by the other surface of the pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet according to any one of claims 1 to 17,
A first peeling film disposed on the first adhesive surface,
Sensitive adhesive sheet having a release film. 19. The method of claim 18, wherein the second surface is a second tacky surface,
And a second peeling film disposed on the second adhesive surface. The method according to claim 18 or 19, wherein the first peeling film has a peeling surface in contact with the first adhesive surface,
The 10-point average roughness of the release face is within 250 nm from the 10-point average roughness of the first adhesive face.

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