JP2021161139A - Adhesive sheet, and method for producing adhesive sheet - Google Patents

Abstract

To provide an adhesive sheet suitable for bonding of various adherends.SOLUTION: An adhesive sheet has a substrate 10, a metal film 20, and a resin layer 30 composed of a plurality of layers disposed on the metal film. At least one of the plurality of layers composing the resin layer is an adhesive layer (X) formed from an adhesive composition (x) that contains an acrylic copolymer (A) having an alkyl (meth)acrylate-derived constitutional unit (a1) and a carboxylated monomer-derived constitutional unit (a2). The adhesive sheet is used for bonding to soda-lime glass.SELECTED DRAWING: Figure 1

Description

The present invention relates to an adhesive sheet and a method for producing the adhesive sheet.

Adhesive sheets with a metal film having a metal film such as aluminum are used for various purposes such as decorative labels and display labels for various products, and conductive sheets for imparting conductivity.
For example, Patent Document 1 describes a conductive layer formed from a metal thin film formed on one surface of a supporting base material and having conductivity in the surface direction, and a thickness direction covering the surface of the conductive layer. A conductive pressure-sensitive adhesive sheet having a conductive pressure-sensitive adhesive layer and an insulating pressure-sensitive adhesive layer covering the other surface of a supporting base material is disclosed.

Japanese Unexamined Patent Publication No. 2013-216794

Such an adhesive sheet with a metal film is attached to various adherends according to each predetermined use. Adhesive sheets suitable for attaching various adherends are required.

The present invention has a base material, a metal film, and a resin layer composed of a plurality of layers laminated on the surface of the metal film, and at least one of the resin layers is an acrylic having a predetermined structural unit. Provided are a pressure-sensitive adhesive sheet used for sticking to soda glass, which is a layer formed from a pressure-sensitive adhesive composition containing a system copolymer, and a method for producing the pressure-sensitive adhesive sheet.
Specific aspects of the present invention are as follows [1] to [10].
[1] An adhesive sheet having a base material, a metal film, and a resin layer composed of a plurality of layers laminated on the surface of the metal film.
Acrylic copolymer (A) in which at least one of the plurality of layers constituting the resin layer has a structural unit (a1) derived from an alkyl (meth) acrylate and a structural unit (a2) derived from a carboxy group-containing monomer. A pressure-sensitive adhesive layer (X) formed from the pressure-sensitive adhesive composition (x) containing the above.
Adhesive sheet used for sticking to soda glass.
[2] The adhesive sheet according to the above [1], wherein the metal film is colored.
[3] The above-mentioned [2], wherein the metal film contains a metal or a metal compound selected from aluminum, chromium, nickel, gold, platinum, silver, tin, copper, iron, palladium, titanium oxide, and titanium nitride. Adhesive sheet.
[4] The pressure-sensitive adhesive sheet according to any one of the above [1] to [3], wherein the thickness of the resin layer is 1 to 100 μm.
[5] Any of the above [1] to [4], wherein the ratio of the thickness of the pressure-sensitive adhesive layer (X) to the thickness of the resin layer [adhesive layer / resin layer] is 0.01 or more. The adhesive sheet described in item 1.
[6] In the pressure-sensitive adhesive composition (x), the content of the structural unit (a2) is 0.1% by mass or more with respect to the total amount of the structural units of the acrylic copolymer (A). The adhesive sheet according to any one of 1] to [5].
[7] The pressure-sensitive adhesive sheet according to any one of the above [1] to [6], wherein the pressure-sensitive adhesive composition (x) further contains a cross-linking agent (B).
[8] In the pressure-sensitive adhesive composition (x), the content of the cross-linking agent (B) is 0.01 to 20.0 parts by mass with respect to 100 parts by mass of the total amount of the acrylic copolymer (A). , The adhesive sheet according to the above [7].
[9] The content of the metal inactivating agent contained in the pressure-sensitive adhesive composition (x) is less than 1 part by mass with respect to 100 parts by mass of the total amount of the acrylic polymer (A). The adhesive sheet according to any one of [8].
[10] The adhesive sheet according to any one of the above [1] to [9], which is used for attaching soda glass to a non-tin surface.

The pressure-sensitive adhesive sheet of one preferred aspect of the present invention is suitable for sticking to soda glass, for example, so-called "evaporation skipping" in which at least a part of a metal film is oxidized and deteriorated by moisture in the atmosphere. It can be effectively suppressed.

It is a schematic cross-sectional view of the pressure-sensitive adhesive sheet which showed an example of the structure of the pressure-sensitive adhesive sheet of one aspect of this invention. It is a schematic cross-sectional view which shows the structure of the pressure-sensitive adhesive sheet of one aspect of this invention which showed an example of the structure of the resin layer composed of a plurality of layers by taking the structure of the pressure-sensitive adhesive sheet 1 shown in FIG. 1A as an example. ..

In addition, in this specification, for example, "(meth) acrylate" is used as a term indicating both "acrylate" and "methacrylate", and the same applies to other similar terms.
Further, the "active ingredient" of the pressure-sensitive adhesive composition (x) or the resin composition (y) is a dilution of an organic solvent or the like among the components contained in the pressure-sensitive adhesive composition (x) or the resin composition (y). It means the component excluding the solvent.

[Structure of adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has a base material, a metal film, and a resin layer composed of a plurality of layers laminated on the surface of the metal film, and at least one of the plurality of layers constituting the resin layer is adherent. The structure is not particularly limited as long as it is the agent layer (X), and may have layers other than these.
For example, FIG. 1 is a schematic cross-sectional view of the pressure-sensitive adhesive sheet showing an example of the structure of the pressure-sensitive adhesive sheet according to one aspect of the present invention. The resin layer of the pressure-sensitive adhesive sheet of the present invention is composed of a plurality of layers, but in the pressure-sensitive adhesive sheet shown in FIG. 1, the plurality of layers constituting the resin layer are collectively described as one layer. There is.

As a specific configuration of the pressure-sensitive adhesive sheet of one aspect of the present invention, as shown in the pressure-sensitive adhesive sheet 1 of FIG. 1A, a metal film 20 is laminated on one surface of the base material 10, and the metal film 20 is further laminated. There is a structure in which the resin layer 30 is laminated on the upper surface, but the present invention is not limited to this.
For example, as shown in the adhesive sheet 2 of FIG. 1B, the metal films 20a and 20b are laminated on both surfaces of the base material 10, and the resin layer 30a is further laminated on the surface of the metal film 20a. The resin layer 30b may be laminated on the surface of the metal film 20b.

Further, in the pressure-sensitive adhesive sheet of one aspect of the present invention, as in the pressure-sensitive adhesive sheet 3 of FIG. 1 (c), a release sheet 40 is further laminated on the surface of the resin layer 30 of the pressure-sensitive adhesive sheet 1 of FIG. 1 (a). It may be configured as such.
Similarly, as in the pressure-sensitive adhesive sheet 4 of FIG. 1 (d), a release sheet 40a is further laminated on the surface of the resin layer 30a of the pressure-sensitive adhesive sheet 2 of FIG. 1 (b), and the release sheet 40a is further laminated on the surface of the resin layer 30b. May be further configured by laminating the release sheets 40b.
The materials of the two release sheets 40a and 40b of the adhesive sheet 4 may be the same or different from each other, but the release force of the release sheet 40a and the release sheet 40b is adjusted to be different. It is preferable to have.

In addition, in the configuration of the pressure-sensitive adhesive sheet 1 of FIG. 1A, a peeling treatment is performed on the surface of the base material 10 opposite to the surface on which the metal film 20 is laminated, and the surface is wound in a roll shape. It may be an adhesive sheet having.
In the pressure-sensitive adhesive sheet of one aspect of the present invention, the base material and the metal film may be directly laminated as in the pressure-sensitive adhesive sheet 1 shown in FIG. 1, and may be directly laminated between the base material and the metal film. It may have a structure having another layer.

The resin layer of the pressure-sensitive adhesive sheet of the present invention is composed of a plurality of layers, and at least one of the plurality of layers is derived from a structural unit (a1) derived from an alkyl (meth) acrylate and a carboxy group-containing monomer. It is a pressure-sensitive adhesive layer (X) formed from the pressure-sensitive adhesive composition (x) containing an acrylic copolymer (A) having a unit (a2).
Here, examples of the resin layer contained in the pressure-sensitive adhesive sheet according to one aspect of the present invention include the following resin layers (i) and (ii).
(I): A resin layer composed of two or more pressure-sensitive adhesive layers (X) that are different from each other.
(Ii): A resin composed of at least one pressure-sensitive adhesive layer (X) and at least one layer (Y) formed of a resin composition (y) that does not correspond to the pressure-sensitive adhesive composition (x). layer.

In the case of (i) above, for example, the pressure-sensitive adhesive layer (X) on the metal film side is desired for the adherend, considering the adhesiveness to the metal film, and the pressure-sensitive adhesive layer (X) on the side to be attached to the adherend is desired. It is preferable to adjust the pressure-sensitive adhesive composition (x) as a forming material in consideration of the adhesive strength of the above.

Further, as the resin layer in the case of (ii) above, for example, the configuration of the resin layer shown in FIG. 2 can be mentioned. FIG. 2 is a schematic diagram showing the structure of the pressure-sensitive adhesive sheet according to one aspect of the present invention, showing an example of the structure of the resin layer composed of a plurality of layers, taking the structure of the pressure-sensitive adhesive sheet 1 shown in FIG. 1 (a) as an example. It is a cross-sectional view.
The structure of the resin layer shown in FIG. 2 can also be applied to the mode of the pressure-sensitive adhesive sheet other than the pressure-sensitive adhesive sheet 1, such as the pressure-sensitive adhesive sheets 2, 3 and 4 in FIG.

First, the resin layer 301 included in the pressure-sensitive adhesive sheet 1a shown in FIG. 2A has a structure in which the pressure-sensitive adhesive layer (X) and the layer (Y) are laminated in this order from the metal film 20 side.
On the other hand, the resin layer of the pressure-sensitive adhesive sheet according to one aspect of the present invention is a layer from the metal film 20 side, as in the pressure-sensitive adhesive sheet 1b shown in FIG. 2B, contrary to the resin layer 301 of the pressure-sensitive adhesive sheet 1a. The structure may be such that the resin layer 302 in which the adhesive layer (X) and the pressure-sensitive adhesive layer (X) are laminated in this order.

Further, in the resin layer of the pressure-sensitive adhesive sheet of one aspect of the present invention, at least one of the pressure-sensitive adhesive layer (X) and the layer (Y) may be a plurality of layers including two or more layers.
For example, the pressure-sensitive adhesive sheet 1c shown in FIG. 2 (c) and the pressure-sensitive adhesive sheet 1d shown in FIG. 2 (d) show a configuration example in which the layer (Y) is a plurality of layers. That is, in the pressure-sensitive adhesive sheet 1c shown in FIG. 2 (c), the pressure-sensitive adhesive layer (X), the first layer (Y), and the second layer (Y) are laminated in this order from the metal film side. It is an adhesive sheet having 303. Further, in the pressure-sensitive adhesive sheet 1d shown in FIG. 2D, a resin layer in which the first layer (Y), the second layer (Y), and the pressure-sensitive adhesive layer (X) are laminated in this order from the metal film side. It is an adhesive sheet having 304. As shown in the adhesive sheets 1c and 1d of FIG. 2, the layers (Y) are formed into two or more multi-layers, and by selecting the material for forming each layer (Y), the physical characteristics of each layer (Y) are characterized. For example, adhesiveness, elastic properties, etc.) can be imparted.
Although FIGS. 2 (c) and 2 (d) show an example in which the layer (Y) is composed of two or more layers, the pressure-sensitive adhesive layer (X) is also composed of two or more layers. You may.

Further, the resin layer of the pressure-sensitive adhesive sheet according to one aspect of the present invention comprises at least one pressure-sensitive adhesive layer (X) and two or more layers (Y) as in the pressure-sensitive adhesive sheet 1e shown in FIG. 2 (e). The structure may be similar to that of the resin layer 305, or the resin layer 306 composed of two or more adhesive layers (X) and at least one layer (Y) as shown in the pressure-sensitive adhesive sheet 1f shown in FIG. 2 (f). It may be configured as follows.
In the adhesive sheet 1e shown in FIG. 2E, one of the two layers (Y) considers the adhesiveness to the metal film, and the other considers the desired adhesive force to the adherend. Therefore, it is preferable to adjust the resin composition which is a forming material.
Similarly, in the pressure-sensitive adhesive sheet 1f shown in FIG. 2 (f), one of the two pressure-sensitive adhesive layers (X) takes into consideration the adhesiveness to the metal film, and the other has the desired adhesive strength to the adherend. It is preferable to prepare the resin composition which is a forming material in consideration of the above.

In general, when an adhesive sheet with a metal film is left to stand for a long period of time while being attached to an adherend, at least a part of the metal film is oxidized by moisture in the atmosphere and deteriorates, so-called "evaporation skipping". May occur. Note that "thin-film deposition skipping" is a phenomenon that can occur not only in a metal vapor deposition film formed by vapor deposition but also in a metal film formed by a method other than vapor deposition. As used herein, the term "thin-film deposition skipping" means a phenomenon in which at least a part of a metal film formed by a method by vapor deposition or a method other than vapor deposition is oxidized and deteriorated.
For example, if vapor deposition skipping occurs in at least a part of a colored metal film having metallic luster, the portion where the vapor deposition skipping occurs is discolored, resulting in an adhesive sheet having an appearance as if there were holes. In this case, when the adhesive sheet is used as a decorative label or a display label, there is an adverse effect that the appearance of these labels is impaired.
Further, even in a transparent metal film such as indium tin oxide (ITO), if vapor deposition skipping occurs, there is a concern that the properties required for the metal film such as conductivity may be deteriorated.

In particular, it has been found by the present inventor that this problem of thin film deposition is likely to occur when the glass is attached to the soda glass, and further when the glass is attached to the non-tin surface of the soda glass.
On the other hand, the pressure-sensitive adhesive sheet according to one aspect of the present invention has a pressure-sensitive adhesive layer (X) formed from a pressure-sensitive adhesive composition (x) containing an acrylic copolymer (A) having a predetermined structural unit, as described later. Since it has a resin layer composed of a plurality of layers containing at least one of, it has a characteristic of being excellent in the effect of suppressing vapor deposition skipping, and even when it is attached to soda glass, the effect of suppressing vapor deposition skipping is high.
Therefore, the adhesive sheet of one aspect of the present invention can be suitably used for sticking to soda glass, and is particularly suitable for sticking to a non-tin surface of soda glass in an environment where vapor deposition skipping is more likely to occur. There is.
Hereinafter, the configuration of each layer of the pressure-sensitive adhesive sheet according to one aspect of the present invention will be described.

<Base material>
The base material contained in the pressure-sensitive adhesive sheet according to one aspect of the present invention is appropriately selected depending on the intended use, and examples thereof include a paper base material, a porous base material such as a non-woven fabric, and a resin film.

Examples of the paper material constituting the paper base material include thin-leaf paper, medium-quality paper, high-quality paper, impregnated paper, coated paper, art paper, sulfated paper, and glassin paper.

Examples of the resin constituting the resin film include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and ethylene-vinyl acetate. Vinyl-based resins such as copolymers and ethylene-vinyl alcohol copolymers; polystyrene; acrylonitrile-butadiene-styrene copolymers; cellulose triacetate; polycarbonate; urethane resins such as polyurethane and acrylic-modified polyurethane; polymethylpentene; polysulfone; Polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; fluorine resin and the like can be mentioned.

These resin films may be composed of only one type of resin or may be composed of two or more types of resins.
Further, the resin film used in one embodiment of the present invention contains various additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an anti-blocking agent, and a colorant in addition to the above-mentioned resin. You may be doing it.

The resin film may be unstretched or may be stretched in a uniaxial direction or a biaxial direction such as vertical or horizontal.
Further, the resin film may be a resin film having a cavity-containing layer containing a cavity inside. A resin film may be formed in which a resin layer containing no cavities is further laminated on at least one surface side of the cavity-containing layer.

The base material used in one embodiment of the present invention may be a single-layer base material made of the above-mentioned paper base material or resin film, and may be a multi-layer base material obtained by laminating two or more kinds selected from the paper base material and the resin film. It may be a base material.
Examples of the multilayer base material include a laminated resin film obtained by laminating two or more kinds of resin films, a laminated base material obtained by laminating a paper base material with a thermoplastic resin such as polyethylene, and the like.

When the base material used in one embodiment of the present invention is a resin film or a laminated base material, the surface of these base materials is subjected to surface treatment such as an oxidation method or an unevenness method, or a primer treatment. May be good.
The oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromium acid oxidation (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
The unevenness method is not particularly limited, and examples thereof include a sandblast method and a solvent treatment method.

The thickness of the base material used in one embodiment of the present invention is preferably 1 to 1000 μm, more preferably 5 to 500 μm, further preferably 10 to 300 μm, still more preferably 15 to 150 μm, and particularly preferably 20 to 120 μm. ..

<Metal film>
The metal film included in the pressure-sensitive adhesive sheet according to one aspect of the present invention is a film containing a metal or a metal compound.
The metal or metal compound constituting the metal film is appropriately selected depending on the intended use. For example, aluminum, chromium, nickel, gold, platinum, silver, tin, copper, iron, palladium, titanium oxide, titanium nitride, etc. Examples thereof include indium tin oxide (ITO).
The metal film contained in the pressure-sensitive adhesive sheet of one aspect of the present invention may be a metal film containing only one type selected from the above metals, or may be a metal film containing two or more types selected from the above metals.

Further, the metal film may be colored or transparent (colorless).
For example, when the pressure-sensitive adhesive sheet of one aspect of the present invention is used as a decorative label or a display label, the metal film becomes colored. The pressure-sensitive adhesive sheet according to one aspect of the present invention has a characteristic of being excellent in suppressing vapor deposition skipping, and is unlikely to cause an adverse effect that the appearance of the label is impaired due to the occurrence of vapor deposition skipping.
When the metal film is colored, the metal film contains a metal or a metal compound selected from aluminum, chromium, nickel, gold, platinum, silver, tin, copper, iron, palladium, titanium oxide, and titanium nitride. Is preferable.

As a method for forming the metal film, the above-mentioned metal or metal compound is vapor-deposited by a PVD (physical vapor deposition) method such as vacuum deposition, sputtering, ion plating, or a film (metal) composed of the above-mentioned metal or metal compound. A method of attaching the foil) using a general adhesive can be mentioned.
When the metal film is a metal vapor-deposited film formed by thin-film deposition, it is general that vapor deposition skipping is more likely to occur. However, the pressure-sensitive adhesive sheet according to one aspect of the present invention has a characteristic of being excellent in the effect of suppressing vapor deposition skipping. Therefore, even when the pressure-sensitive adhesive sheet of one aspect of the present invention has a metal-deposited film as the metal film, it is possible to effectively suppress the vapor deposition skipping that may occur on the metal-deposited film.

The film thickness of the metal film of the pressure-sensitive adhesive sheet according to one aspect of the present invention is preferably 1 to 5000 nm, more preferably 5 to 1000 nm, still more preferably 10 to 500 nm, and even more preferably 20 to 300 nm.

<Resin layer>
The resin layer of the pressure-sensitive adhesive sheet of the present invention is composed of a plurality of layers, and at least one of the plurality of layers is derived from a structural unit (a1) derived from an alkyl (meth) acrylate and a carboxy group-containing monomer. It is a pressure-sensitive adhesive layer (X) formed from the pressure-sensitive adhesive composition (x) containing an acrylic copolymer (A) having a structural unit (a2).

In various studies, the present inventor has found that when the pressure-sensitive adhesive sheet with a metal film is attached to soda glass, particularly when it is attached to the non-tin surface of soda glass, thin-film deposition skipping is likely to occur. .. The reason for this is thought to be as follows.
Soda glass, together with quartz sand (SiO _2), sodium carbonate _(Na 2 _CO 3), calcium carbonate (CaCO ₃₎ and magnesium carbonate (CaCO ₃₎ in which metal salt by mixing the prepared melts such as be. Therefore, soda glass contains metal oxides derived from metal salts such as sodium oxide (Na ₂ O), calcium oxide (CaO) and magnesium oxide (MgO). The metal ions derived from these metal oxides migrate to the pressure-sensitive adhesive layer and the metal film of the pressure-sensitive adhesive sheet with a metal film attached to the surface of the soda glass to promote the oxidation of the metal film, resulting in vapor deposition. It is presumed that jumping will occur.
Then, it was found by the present inventor that when the pressure-sensitive adhesive sheet with a metal film is attached to the non-tin surface of the soda glass, the vapor deposition skipping is more likely to occur than when the adhesive sheet with the metal film is attached to the tin surface. Therefore, it is considered that the metal ions derived from the above-mentioned metal oxides are more likely to be transferred to the metal film of the pressure-sensitive adhesive sheet on the non-tin surface.

Therefore, the present inventor has a pressure-sensitive adhesive composition in which at least one of the plurality of layers constituting the resin layer contains an acrylic copolymer (A) having a structural unit (a2) derived from a carboxyl group-containing monomer. By forming the pressure-sensitive adhesive layer (X) formed from the substance (x), an attempt was made to suppress the transfer of metal ions derived from the metal oxide contained in the soda glass to the metal film.
That is, on the adhesive surface of the pressure-sensitive adhesive layer with the soda glass, the metal ion derived from the metal oxide contained in the soda glass is contained in the carboxy group (-) of the constituent unit (a2) of the acrylic copolymer (A). It was speculated that COOH) could capture and suppress the transfer to the metal film. Then, based on the guess, by using the acrylic copolymer (A) having the structural unit (a2) containing the carboxy group for the formation of the pressure-sensitive adhesive layer (X), the pressure-sensitive adhesive that can effectively suppress the vapor deposition skipping. It was found that it could be a sheet, and the adhesive sheet of the present invention was completed based on that knowledge.

In the resin layer composed of a plurality of layers of the pressure-sensitive adhesive sheet of one aspect of the present invention, the position where the pressure-sensitive adhesive layer (X) is laminated is not particularly limited. For example, as shown in FIG. 2, a position where the metal film is directly laminated (for example, the adhesive sheets 1a, 1c, 1f, etc. in FIG. 2) and a position where an adhesive surface to be attached to the adherend is formed (for example, FIG. The adhesive sheet 1b, 1d, 1f, etc. of 2) and the position where the metal film and the adherend do not come into direct contact with each other (for example, the adhesive sheet 1e of FIG. 2) may be used.
That is, the pressure-sensitive adhesive layer (X) formed from the pressure-sensitive adhesive composition (x) may be present at any position of the resin layer. In the pressure-sensitive adhesive layer (X) existing at any position of the resin layer, the carboxy group (-COOH) of the structural unit (a2) in the pressure-sensitive adhesive layer (X) is a metal derived from a metal oxide. It can capture ions and suppress the transfer to the metal film.

On the other hand, the layers (Y) other than the pressure-sensitive adhesive layer (X) constituting the resin layer of the pressure-sensitive adhesive sheet of one aspect of the present invention impart desired properties without being restricted from the viewpoint of suppressing vapor deposition skipping. From the viewpoint, various forming materials can be designed.
For example, in the structure of the pressure-sensitive adhesive sheet 1b shown in FIG. 2B, the resin composition (y) which is the material for forming the layer (Y) has high adhesiveness from the viewpoint of further improving the adhesive strength with the adherend. Adhesive resin can be selected.
Further, in the structure of the pressure-sensitive adhesive sheet 1e shown in FIG. 2 (e), the resin composition (y) as the material for forming the layer (Y) has high elasticity from the viewpoint of forming the pressure-sensitive adhesive sheet with high shape retention and elasticity. The resin of the rate can be selected.
Further, when the layer (Y) is a plurality of layers as in the pressure-sensitive adhesive sheet 1c shown in FIG. 2 (c), the first layer (Y) laminated on the pressure-sensitive adhesive layer (X). Is preferably formed from the resin composition (y) containing a resin having a high elastic modulus from the viewpoint of forming an adhesive sheet having high shape retention and elasticity. On the other hand, the second layer (Y) on the side to be attached to the adherend is from the resin composition (y) containing a highly adhesive adhesive resin from the viewpoint of further improving the adhesive strength with the adherend. It is preferable to form.
Similarly, in the case of the adhesive sheet 1d shown in FIG. 2D, the first layer (Y) on the metal film side is made of a highly adhesive adhesive resin from the viewpoint of improving the adhesion to the metal film. It is preferably formed from the containing resin composition (y). Further, the second layer (Y) located between the first layer (Y) and the adhesive layer (X) has a high elastic modulus from the viewpoint of forming an adhesive sheet having high shape retention and elasticity. It is preferably formed from the resin composition (y) containing a resin.
In any of the above examples, since the pressure-sensitive adhesive layer (X) is present in the resin layer, the vapor deposition skips when examining the resin composition (y) which is the material for forming the layer (Y). It is not necessary to consider from the viewpoint of suppressing the amount of resin.

The thickness of the resin layer of the pressure-sensitive adhesive sheet according to one aspect of the present invention is appropriately adjusted depending on the application and the like, but is preferably 1 to 100 μm, more preferably 2 to 80 μm, still more preferably 3 to 60 μm, still more preferably. Is 5 to 50 μm.

In the pressure-sensitive adhesive sheet of one aspect of the present invention, the ratio of the thickness of the pressure-sensitive adhesive layer (X) to the thickness of the resin layer [adhesive layer (X) / resin layer] is excellent due to the effect of suppressing vapor deposition skipping. From the viewpoint of forming an adhesive sheet, it is preferably 0.01 or more, more preferably 0.10 or more, still more preferably 0.20 or more, still more preferably 0.30 or more, and particularly preferably 0.40 or more.
Further, the ratio of the thickness of the pressure-sensitive adhesive layer (X) to the thickness of the resin layer [adhesive layer (X) / resin layer] is not particularly limited in its upper limit, and the characteristics to be imparted to the pressure-sensitive adhesive sheet and the like. It is appropriately set according to, for example, 1 or less, 0.99 or less, 0.95 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less, 0. It may be .65 or less, 0.60 or less, 0.55 or less, or 0.50 or less.

Hereinafter, the pressure-sensitive adhesive composition (x) and the resin composition (y), which are materials for forming the pressure-sensitive adhesive layer (X) and the layer (Y) constituting the resin layer of the present invention, will be described.

[Adhesive composition (x)]
The pressure-sensitive adhesive composition (x), which is a material for forming the pressure-sensitive adhesive layer (X), contains an acrylic copolymer (A), but preferably further contains a cross-linking agent (B).
In the pressure-sensitive adhesive composition (x) used in one embodiment of the present invention, the total content of the components (A) and (B) is based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x). It is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 60 to 100% by mass, still more preferably 65 to 100% by mass, and particularly preferably 70 to 100% by mass.

Further, the pressure-sensitive adhesive composition (x) used in one aspect of the present invention may further contain a pressure-sensitive adhesive (C), and contains additives for pressure-sensitive adhesives other than the components (A) to (C). You may.
Hereinafter, each component contained in the pressure-sensitive adhesive composition (x) used in one aspect of the present invention will be described.

<Component (A): Acrylic copolymer>
The acrylic copolymer (A) used in one embodiment of the present invention is a structural unit (a1) derived from an alkyl (meth) acrylate (hereinafter, also referred to as “monomer (a1 ′)”) and a carboxy group-containing monomer (hereinafter, also referred to as “monomer (a1 ′)”). , Also referred to as "monomer (a2')").
The acrylic copolymer (A) may be used alone or in combination of two or more.
Further, the acrylic copolymer (A) used in one aspect of the present invention may be an emulsion type polymer or a non-emulsion type polymer, but is preferably a non-emulsion type polymer.
Further, the form of copolymerization of the acrylic copolymer (A) is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer.

The mass average molecular weight (Mw) of the acrylic copolymer (A) used in one embodiment of the present invention is preferably 50,000 to 2 million, more preferably 100,000 to 1.8 million, still more preferably 200,000 to 1.5 million. Even more preferably, it is 250,000 to 1.2 million, and particularly preferably 300,000 to 1 million.
In the present specification, the mass average molecular weight (Mw) is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, and is specifically measured based on the method described in Examples. Value.

In the pressure-sensitive adhesive composition (x) used in one embodiment of the present invention, the content of the acrylic copolymer (A) is based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x). It is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
The content of the acrylic copolymer (A) may be 100% by mass or less with respect to the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x), but the cross-linking agent ( When B) is contained, it is preferably 99.95% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.5% by mass or less, still more preferably 99.0% by mass or less, particularly. It is preferably 98.5% by mass or less.
That is, the content of the acrylic copolymer (A) is preferably 30 to 99.99% by mass, more preferably 30% by mass, based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition (x). It is 40 to 99.95% by mass, more preferably 50 to 99.90% by mass, still more preferably 60 to 99.50% by mass, and particularly preferably 70 to 99.00% by mass.

The acrylic copolymer (A) used in one embodiment of the present invention has a common weight having a structural unit (a3) derived from a functional group-containing monomer other than the carboxy group (hereinafter, also referred to as “monomer (a3')”). It may be a coalescence, and a structural unit (a4) derived from a monomer other than the monomers (a1'), (a2') and (a3') (hereinafter, also referred to as "monomer (a4')") is used. It may be a copolymer having.

In the acrylic copolymer (A) used in one aspect of the present invention, the total content of the structural units (a1) and (a2) is the total mass (100) of the structural units of the acrylic copolymer (A). With respect to (% by mass), preferably 35 to 100% by mass, more preferably 45 to 100% by mass, more preferably 55 to 100% by mass, still more preferably 65 to 100% by mass, still more preferably 75 to 100% by mass. , More preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass.
Hereinafter, the monomers and constituent units constituting the acrylic copolymer (A) will be described.

[Monomer (a1'), constituent unit (a1)]
The number of carbon atoms of the alkyl group contained in the monomer (a1') is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 16, still more preferably 1 to 12, and particularly preferably 4 to 8. be.
The alkyl group contained in the monomer (a1') may be a straight chain alkyl group or a branched chain alkyl group.

Examples of the monomer (a1') include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate (n-propyl (meth) acrylate, i-propyl (meth) acrylate), and butyl (meth) acrylate. (N-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate), pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Examples thereof include acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate.
These monomers (a1') may be used alone or in combination of two or more.

The acrylic copolymer (A) used in one embodiment of the present invention is an alkyl (meth) acrylate having an alkyl group having 4 to 8 carbon atoms as a structural unit (a1) (hereinafter, “monomer (a11 ′)). It is preferable to have a structural unit (a11) derived from "also referred to as".

The monomer (a11') may contain at least one selected from butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Preferably, it contains butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate, and even more preferably butyl (meth) acrylate.

The content ratio of the structural unit (a11) is preferably 60 to 100% by mass, more preferably 70 to 70 to the total amount (100% by mass) of the structural unit (a1) contained in the acrylic copolymer (A). It is 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.

In the acrylic copolymer (A) used in one aspect of the present invention, the content of the structural unit (a1) is based on the total amount (100% by mass) of the structural units of the acrylic copolymer (A). It is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, and preferably 99.9% by mass or more. % Or less, more preferably 99.5% by mass or less, still more preferably 99.0% by mass or less, still more preferably 98.0% by mass or less, and particularly preferably 97.0% by mass or less.
That is, the content of the structural unit (a1) is preferably 30 to 99.9% by mass, more preferably 40 to 40% by mass, based on the total amount (100% by mass) of the structural unit of the acrylic copolymer (A). It is 99.5% by mass, more preferably 50 to 99.0% by mass, still more preferably 60 to 98.0% by mass, and particularly preferably 70 to 97.0% by mass.

[Monomer (a2'), constituent unit (a2)]
Examples of the monomer (a2') include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid; 2- Examples thereof include carboxylethyl (meth) acrylate.
These monomers (a2') may be used alone or in combination of two or more.

The monomer (a2') used in one aspect of the present invention preferably contains an ethylenically unsaturated monocarboxylic acid, and more preferably contains (meth) acrylic acid.
The content of the structural unit (a2) is adjusted so as to satisfy the above requirement (I), and the suitable range is also as described above.

In the acrylic copolymer (A) used in one embodiment of the present invention, the content of the structural unit (a2) is based on the total amount (100% by mass) of the structural units of the acrylic copolymer (A). It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2.0% by mass. % Or more, particularly preferably 3.0% by mass or more.
Further, the content of the constituent unit (a2) is preferably 50% by mass or less, more preferably 50% by mass or less, based on the total amount of the constituent units of the acrylic copolymer (A) from the viewpoint of forming an adhesive sheet having excellent adhesive strength. Is 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
That is, in one aspect of the present invention, the content of the structural unit (a2) is preferably 0.1 to 50% by mass, more preferably 0, based on the total amount of the structural units of the acrylic copolymer (A). .5 to 40% by mass, more preferably 1.0 to 35% by mass, still more preferably 1.5 to 30% by mass, even more preferably 2.0 to 25% by mass, particularly preferably 3.0 to 20% by mass. %.

[Monomer (a3'), constituent unit (a3)]
The acrylic copolymer (A) used in one embodiment of the present invention may be a copolymer having a structural unit (a3) derived from a functional group-containing monomer (monomer (a3')) other than the carboxy group. ..
Examples of the monomer (a3') include a hydroxy group-containing monomer and an epoxy group-containing monomer.
These monomers (a3') may be used alone or in combination of two or more.

Examples of the hydroxy-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate. ) Hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol can be mentioned.
The alkyl group of the hydroxyalkyl (meth) acrylates has preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

Examples of the epoxy-containing monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate. Epoxy group-containing (meth) acrylic acid ester such as glycidyl crotonate, allyl glycidyl ether and the like.

In the acrylic copolymer (A) used in one embodiment of the present invention, the content of the structural unit (a3) is based on the total amount (100% by mass) of the structural units of the acrylic copolymer (A). It is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
The content of the structural unit (a3) is not particularly limited to the lower limit value, and is 0% by mass or more, 0.01% by mass, based on the total amount (100% by mass) of the structural unit of the acrylic copolymer (A). It may be mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, 0.5 mass% or more.
Regarding the content of the structural unit (a3), the above lower limit and upper limit can be arbitrarily selected and combined.

[Monomer (a4'), constituent unit (a4)]
The acrylic copolymer (A) used in one embodiment of the present invention is a structural unit derived from a monomer (monomer (a4')) other than the monomers (a1'), (a2') and (a3'). It may be a copolymer having a4).
The monomer (a4') is not particularly limited, and examples thereof include olefins such as ethylene, propylene and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, and diene monomers such as butadiene, isoprene and chloroprene. Examples thereof include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholine, and N-vinylpyrrolidone.
These monomers (a4') may be used alone or in combination of two or more.

In the acrylic copolymer (A) used in one aspect of the present invention, the content of the structural unit (a4) is based on the total amount (100% by mass) of the structural units of the acrylic copolymer (A). It is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, still more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass.

<Other adhesive resins>
The pressure-sensitive adhesive composition (x) used in one aspect of the present invention may further contain a pressure-sensitive adhesive resin other than the component (A) as long as the effects of the present invention are not impaired.
The other adhesive resin may be a resin having adhesiveness by itself, but for example, it can be polymerized with urethane-based resin, rubber-based resin, olefin-based resin, silicone-based resin, and these resins. Examples thereof include a curable resin into which a group has been introduced.
These other adhesive resins may be used alone or in combination of two or more.
Further, the other adhesive resin may be an emulsion type resin or a non-emulsion type resin, but a non-emulsion type resin is preferable.

The mass average molecular weight (Mw) of the other adhesive resin used in one aspect of the present invention is preferably 10,000 to 2 million, more preferably 20,000 to 1.8 million, and even more preferably 30,000 to 1.5 million.

In the pressure-sensitive adhesive composition (x) used in one aspect of the present invention, the content of the pressure-sensitive resin other than the component (A) is 100, which is the total mass of the component (A) contained in the pressure-sensitive adhesive composition (x). With respect to parts by mass, preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, still more preferably 0 to 10 parts by mass, still more preferably 0 to 5 parts by mass. Even more preferably, it is 0 to 1 part by mass, and particularly preferably 0 to 0.1 part by mass.

<Component (B): Crosslinking agent>
The pressure-sensitive adhesive composition (x) used in one aspect of the present invention preferably further contains a cross-linking agent (B).
By preparing the pressure-sensitive adhesive composition (x) containing the cross-linking agent (B) together with the component (A), the cohesive force in the pressure-sensitive adhesive layer can be enhanced, and a pressure-sensitive adhesive sheet having a high pressure-sensitive adhesive force can be obtained. Further, in a high temperature and high humidity environment where vapor deposition skipping is more likely to occur, even when the glass is left to stand for a long period of time while being attached to soda glass, the vapor deposition skipping can be suppressed more effectively.

Examples of the cross-linking agent (B) used in one embodiment of the present invention include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, imine-based cross-linking agents, and metal chelate-based cross-linking agents.
These cross-linking agents (B) may be used alone or in combination of two or more.

Examples of the isocyanate-based cross-linking agent include tolylene diisocyanate compounds such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate; Range isocyanate compounds; diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2 , 4'-diisocyanate, lysine isocyanate and the like.
In addition, a trimer of these organic polyvalent isocyanate compounds, a terminal isocyanate urethane prepolymer obtained by reacting these organic polyvalent isocyanate compounds with a polyol compound, and the like can also be used.

Examples of the epoxy-based cross-linking agent include bisphenol A type epoxy compound, bisphenol F type epoxy compound, 1,3-bis (N, N-diglycidylaminomethyl) toluene, N, N, N', N'-tetraglycidyl. -4,4-diaminodiphenylmethane and the like can be mentioned.

Examples of the imine-based cross-linking agent include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinyl propionate, and trimethylolmethane-tri. Examples thereof include -β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxyamide) triethylene melamine and the like.

Examples of the metal chelate-based cross-linking agent include coordination compounds of polyvalent metals such as aluminum chelate-based compounds such as trisethylacetoacetate aluminum, ethylacetacetate aluminum diisopropyrate, and trisacetylacetonate aluminum.

The cross-linking agent (B) used in one embodiment of the present invention preferably contains at least one selected from an isocyanate-based cross-linking agent and a metal chelate-based cross-linking agent, and more preferably contains at least an isocyanate-based cross-linking agent. It is more preferable to contain at least an isocyanate-based compound.

When the pressure-sensitive adhesive composition (x) used in one embodiment of the present invention contains a cross-linking agent (B), the content of the cross-linking agent (B) is based on 100 parts by mass of the total amount of the acrylic copolymer (A). It is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, more preferably 0.10 part by mass or more, still more preferably 0.50 part by mass or more, still more preferably 0. 70 parts by mass or more, particularly preferably 1.00 parts by mass or more, preferably 20.0 parts by mass or less, more preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, still more preferable. Is 8.0 parts by mass or less, more preferably 6.0 parts by mass or less, and particularly preferably 4.5 parts by mass or less.
That is, in one aspect of the present invention, the content of the cross-linking agent (B) is preferably 0.01 to 20.0 parts by mass, more preferably 0.01 to 20.0 parts by mass, based on 100 parts by mass of the total amount of the acrylic copolymer (A). Is 0.05 to 15.0 parts by mass, more preferably 0.10 to 10.0 parts by mass, still more preferably 0.50 to 8.0 parts by mass, still more preferably 0.70 to 6.0 parts by mass. , Particularly preferably 1.00 to 4.5% by mass.

<Adhesive imparting agent (C)>
The pressure-sensitive adhesive composition (x) used in one aspect of the present invention may further contain a pressure-sensitive adhesive (C).
In the present specification, the tackifier is a component that supplementarily improves the tackiness of the acrylic copolymer (A), which is a tacky resin, and usually has a mass average molecular weight (Mw) of 10,000. It is less than an oligomer and is distinguished from the above-mentioned adhesive resin containing the acrylic copolymer (A).
The mass average molecular weight (Mw) of the tackifier (C) used in one aspect of the present invention is preferably 400 to 4000, more preferably 800 to 1500.

Examples of the tackifier (C) used in one embodiment of the present invention include rosin-based resin, terpene-based resin, styrene-based resin, hydrocarbon-based resin, and hydrogenated resin obtained by hydrogenating these resins. ..
These tackifiers (C) may be used alone or in combination of two or more.

Examples of the rosin-based resin include a rosin resin, a rosin ester resin, a rosin phenol resin, and the like, and a hydrogenated rosin-based resin obtained by hydrogenating these resins may be used.
The terpene-based resin may be a compound having a structural unit derived from isopene, and examples thereof include terpene resins, aromatic-modified terpene resins, and terpene phenol-based resins, and hydrogenation of these resins. It may be a terpene resin.
Examples of the styrene-based resin include a resin obtained by copolymerizing a styrene-based monomer such as α-methylstyrene or β-methylstyrene with an aliphatic monomer, and hydrogenated styrene obtained by hydrogenating the resin. It may be a styrene resin.
Examples of the hydrocarbon resin include a C5 hydrocarbon resin obtained by copolymerizing C5 fractions such as penten, isoprene, piperin, and 1.3-pentadiene produced by thermal decomposition of petroleum naphtha; heat of petroleum naphtha. Examples thereof include C9-based hydrocarbon resins obtained by copolymerizing C9 fractions such as inden and vinyl toluene produced by decomposition; and hydrocarbon resins obtained by hydrogenating these.

The softening point of the tackifier (C) used in one embodiment of the present invention is preferably 70 to 170 ° C, more preferably 80 to 160 ° C, still more preferably 85 to 150 ° C, still more preferably 90 to 140 ° C. be.
In this specification, the softening point of the tackifier (C) means a value measured in accordance with JIS K2531.
When two or more kinds of tackifiers are used in combination, it is preferable that the weighted average value calculated from the softening point and the blending amount ratio of each tackifier is in the above range.

When the pressure-sensitive adhesive composition (x) used in one aspect of the present invention contains the pressure-sensitive adhesive (C), the content of the pressure-sensitive adhesive (C) is the acrylic type contained in the pressure-sensitive adhesive composition (x). With respect to 100 parts by mass of the total amount of the copolymer (A), preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 20 to 180 parts by mass, still more preferably 30 to 150 parts by mass. Is.

<Additives for adhesives>
The pressure-sensitive adhesive composition (x) used in one aspect of the present invention further contains an additive for a pressure-sensitive adhesive other than the cross-linking agent (B) and the pressure-sensitive adhesive (C) as long as the effects of the present invention are not impaired. May be good.
Examples of such additives for adhesives include plasticizers (liquid resins, liquid paraffins, etc.), compatibilizers, wetting agents, thickeners, antifoaming agents, ultraviolet absorbers, antioxidants, fillers, and the like. Examples thereof include rust preventives, antibacterial agents, insect repellents, fragrances, pigments, dyes, curing agents, curing aids, catalysts and the like.
Each of these additives may be used alone or in combination of two or more.

When the pressure-sensitive adhesive composition (x) used in one aspect of the present invention contains these pressure-sensitive adhesive additives, the content of each of the pressure-sensitive adhesive additives is appropriately set according to the type of the additive. However, with respect to 100 parts by mass of the total amount of the acrylic copolymer (A), preferably 0.01 to 40 parts by mass, more preferably 0.05 to 30 parts by mass, and further preferably 0.1 to 20 parts by mass. Parts, more preferably 0.2 to 10 parts by mass.

The pressure-sensitive adhesive composition (x) according to one aspect of the present invention may contain a metal inactivating agent, but since it is a persistent substance itself, it is metal inactivated from the viewpoint of the environment. The smaller the content of the agent, the more preferable.
The specific content of the metal inactivating agent is preferably less than 1 part by mass, more preferably less than 0.1 part by mass, still more preferably, with respect to 100 parts by mass of the total amount of the acrylic copolymer (A). Is less than 0.01 parts by mass, more preferably less than 0.001 parts by mass, particularly preferably less than 0.0001 parts by mass or 0 parts by mass (that is, it does not contain a metal inactivating agent).

Examples of the metal inactivating agent include benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, 5-chlorobenzotriazole, triltriazole, potassium salt of triltriazole, and 3- (N-salicyloyl) amino. Examples thereof include -1,2,4-triazole and 2- (2'-hydroxy-5-methylphenyl) benzotriazole.

<Organic solvent>
The pressure-sensitive adhesive composition (x) used in one aspect of the present invention may be further diluted with an organic solvent to form a solution from the viewpoint of facilitating the formation of a coating film and improving workability.
Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, isopropanol and the like.
These organic solvents may be used alone or in combination of two or more.
As these organic solvents, the organic solvent used in the synthesis of the acrylic copolymer (A) may be used as it is, or other than the organic solvent used in the synthesis of the acrylic copolymer (A). One or more organic solvents may be added.

The concentration of the active ingredient of the pressure-sensitive adhesive composition (x) used in one embodiment of the present invention is preferably 5 to 80% by mass, more preferably 5 to 80% by mass, based on the total amount (100% by mass) of the pressure-sensitive adhesive composition (x). Is 10 to 70% by mass, more preferably 15 to 60% by mass.

[Resin composition (y)]
The pressure-sensitive adhesive composition (y), which is the material for forming the layer (Y), preferably contains at least one resin component.
In the present specification, the “resin component” means a polymer having one or more repeating units and having a mass average molecular weight of 10,000 or more.
The mass average molecular weight (Mw) of the resin component used in one embodiment of the present invention is appropriately set according to the type of resin, but is preferably 10,000 to 2 million, more preferably 15,000 to 1.5 million, and further. It is preferably 20,000 to 1.2 million.

In the resin composition (y) used in one aspect of the present invention, the content of the resin component is preferably 30% by mass or more with respect to the total amount (100% by mass) of the active ingredient of the resin composition (y). It is more preferably 40% by mass or more, further preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The resin composition (y) used in one embodiment of the present invention may contain a cross-linking agent and various additives depending on the type of the resin component in addition to the resin component.
For example, as the cross-linking agent, the same one as the component (B) contained in the above-mentioned pressure-sensitive adhesive composition (x) can be mentioned.
The content of the cross-linking agent is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin component contained in the resin composition (y). More preferably, it is 0.10 to 15 parts by mass.

The resin composition (y) according to one aspect of the present invention may contain a metal inactivating agent, but since it is a persistent substance itself, it is a metal inactivating agent from the viewpoint of the environment. The smaller the content of, the more preferable.
The specific content of the metal inactivating agent is preferably less than 1 part by mass, more preferably less than 0.1 part by mass, based on 100 parts by mass of the total amount of the resin component contained in the resin composition (y). It is more preferably less than 0.01 parts by mass, even more preferably less than 0.001 parts by mass, and particularly preferably less than 0.0001 parts by mass or 0 parts by mass (that is, it does not contain a metal inactivating agent).

Since the resin component used in one aspect of the present invention is appropriately selected according to the function of the layer (Y), it may be, for example, an adhesive resin or a non-adhesive resin.
In this specification, whether or not it corresponds to "adhesive resin" or "non-adhesive resin" can be confirmed by, for example, the following procedures (1) to (4).
Procedure (1): A 20 μm-thick resin layer formed only from the target resin is provided on a 50 μm-thick polyethylene terephthalate (PET) film, and a test piece cut into a size of 300 mm in length × 25 mm in width is cut. To make.
-Procedure (2): In an environment of 23 ° C. and 50% RH (relative humidity), the exposed side surface of the resin layer of the test piece was attached to a stainless steel plate (SUS304 No. 360 polishing). Let stand for 24 hours in the environment.
-Procedure (3): After standing, the adhesive strength is increased at a tensile speed of 300 mm / min by the 180 ° peeling method based on JIS Z0237: 2000 in an environment of 23 ° C. and 50% RH (relative humidity). taking measurement.
-Procedure (4): If the measured adhesive strength is 0.1 N / 25 mm or more, the target resin is judged to be "adhesive resin". On the other hand, if the measured adhesive strength is less than 0.1 N / 25 mm, the target resin is determined to be a "non-adhesive resin".

Hereinafter, the adhesive resin and the non-adhesive resin contained in the resin composition (y) will be described.

(Adhesive resin)
Examples of the adhesive resin used in one embodiment of the present invention include acrylic copolymers, urethane resins, rubber resins, olefin resins, silicone resins, and resins having no structural unit (a2). Examples thereof include a curable resin into which a polymerizable group has been introduced.
These adhesive resins may be used alone or in combination of two or more.
The adhesive resin may be an emulsion type resin or a non-emulsion type resin, but is preferably a non-emulsion type resin.
Further, when the adhesive resin is a copolymer, the form of the copolymer is not particularly limited and may be any of a random copolymer, a block copolymer, and a graft copolymer.

When the resin composition (y) used in one aspect of the present invention contains an adhesive resin, the content of the adhesive resin is based on the total amount (100% by mass) of the active ingredient of the resin composition (y). It is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

When the resin composition (y) used in one aspect of the present invention contains a pressure-sensitive adhesive resin, it may further contain a cross-linking agent or a pressure-sensitive adhesive, and contains other additives for a pressure-sensitive adhesive. You may.
The cross-linking agent, tackifier, and adhesive additive contained in the resin composition (y) are the same as the cross-linking agent, tackifier, and adhesive additive contained in the pressure-sensitive adhesive composition (x). Can be used.

It should be noted that these cross-linking agents, tackifiers, and pressure-sensitive adhesive additives have characteristics required for the layer (Y), which is the pressure-sensitive adhesive layer formed from the resin composition (y) (for example, interlayer adhesion with a metal film). The type of each component used and the content of each component are appropriately adjusted so as to exhibit properties, adhesiveness to the adherend, removability, etc.).
As a specific example, the content of the cross-linking agent is preferably 0.01 to 20.0 parts by mass, more preferably 0, based on 100 parts by mass of the total amount of the adhesive resin contained in the resin composition (y). .05 to 15.0 parts by mass, more preferably 0.10 to 10.0 parts by mass.
The content of the tackifier is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the adhesive resin contained in the resin composition (y). It is ~ 180 parts by mass, more preferably 30 to 150 parts by mass.
The content of each of the adhesive additives is appropriately set according to the type of the additive, but is preferably 0. With respect to 100 parts by mass of the total amount of the adhesive resin contained in the resin composition (y). It is 01 to 40 parts by mass, more preferably 0.05 to 30 parts by mass, still more preferably 0.1 to 20 parts by mass, and even more preferably 0.2 to 10 parts by mass.

(Non-adhesive resin)
Examples of the non-adhesive resin used in one embodiment of the present invention include acrylic urethane-based resin; olefin-based resin; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol co-weight. Vinyl-based resins such as coalesced; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene-based resins; acrylonitrile-butadiene-styrene copolymers; cellulose triacetate; polycarbonate-based resins; polymethylpentene; polysulfones; Polyether ether ketone; polyether sulfone; polyphenylene sulfide; polyimide resin such as polyetherimide and polyimide; polyamide resin; acrylic resin; fluororesin; and curable resin in which a polymerizable group is introduced into these resins. Can be mentioned.
These non-adhesive resins may be used alone or in combination of two or more.
The non-adhesive resin may be an emulsion type resin or a non-emulsion type resin, but is preferably a non-emulsion type resin.
Further, when the non-adhesive resin is a copolymer, the form of the copolymer is not particularly limited and may be any of a random copolymer, a block copolymer, and a graft copolymer.

When the resin composition (y) used in one aspect of the present invention contains a non-adhesive resin, the content of the non-adhesive resin is based on the total amount (100% by mass) of the active ingredient of the resin composition (y). It is preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. be.

The non-adhesive resin contained in the resin composition (y) used in one aspect of the present invention preferably contains one or more selected from acrylic urethane-based resins and olefin-based resins.

Examples of the acrylic urethane resin include a reaction product of an acrylic polyol compound and an isocyanate compound, a linear urethane prepolymer having ethylenically unsaturated groups at both ends, and a vinyl compound containing a (meth) acrylic acid ester. Examples thereof include a copolymer obtained by polymerizing.
The mass average molecular weight (Mw) of the acrylic urethane resin is preferably 2,000 to 500,000, more preferably 4,000 to 300,000, still more preferably 5,000 to 200,000, and even more preferably 10,000 to 10,000. It is 150,000.

The olefin resin is a polymer having at least a structural unit derived from the olefin monomer.
As the olefin monomer, α-olefin having 2 to 8 carbon atoms is preferable, one or more selected from ethylene, propylene, butylene, isobutylene, and 1-hexene is more preferable, and one or more selected from ethylene and propylene are more preferable. More preferred.

Specific olefinic resins, for example, ultra low density polyethylene (VLDPE, density: 880 kg / ^{m 3} or more 910 kg / ^m less than ^3), low density polyethylene (LDPE, density: 910 kg / ^{m 3} or more 915 kg / ^m less than ³ ), Medium density polyethylene (MDPE, density: 915 kg / m ³ or more and less than 942 kg / m ³ ), high density polyethylene (HDPE, density: 942 kg / m ³ or more), linear low density polyethylene and other polyethylene resins; polypropylene resin (PP); Polyethylene resin (PB); Ethylene-propylene copolymer; Olefin-based elastomer (TPO); Ethylene-vinyl acetate copolymer (EVA); Ethylene-propylene- (5-ethylidene-2-norbornene), etc. Olefin-based ternary copolymer; and the like.
In addition, these olefin-based resins may be modified olefin-based resins further subjected to one or more types of modification selected from acid modification, hydroxyl group modification, and acrylic modification.

The mass average molecular weight (Mw) of the olefin resin is preferably 2,000 to 1,000,000, more preferably 10,000 to 500,000, further preferably 20,000 to 400,000, and even more preferably 50,000 to 300,000. be.

When the resin composition (y) used in one aspect of the present invention contains a non-adhesive resin, it may further contain a cross-linking agent or a catalyst. In particular, in the case of the resin composition (y) containing an acrylic urethane-based resin as the non-adhesive resin, it is preferable to further contain a cross-linking agent and a catalyst.
The cross-linking agent and the catalyst may be used alone or in combination of two or more.

Examples of the cross-linking agent include the same cross-linking agents as those contained in the pressure-sensitive adhesive composition (x) described above, but isocyanate-based cross-linking agents are preferable.
As the isocyanate-based cross-linking agent, an aliphatic isocyanate compound is preferable, an aliphatic diisocyanate compound is more preferable, and pentamethylene diisocyanate, hexamethylene diisocyanate, or heptamethylene diisocyanate is further preferable.
The content of the cross-linking agent is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and further preferably 3 with respect to 100 parts by mass of the total amount of the non-adhesive resin contained in the resin composition (y). ~ 15 parts by mass.

As the catalyst, a metal-based catalyst is preferable, and a metal-based catalyst excluding a tin-based compound having a butyl group is more preferable.
Examples of the metal-based catalyst include tin-based catalysts, bismuth-based catalysts, titanium-based catalysts, vanadium-based catalysts, zirconium-based catalysts, aluminum-based catalysts, nickel-based catalysts, etc., and tin-based catalysts or bismuth-based catalysts are preferable. , Tin-based catalysts or bismuth-based catalysts excluding tin-based compounds having a butyl group are more preferable.
The content of the catalyst is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and further, based on 100 parts by mass of the total amount of the non-adhesive resin contained in the resin composition (y). It is preferably 0.1 to 2 parts by mass.

When the resin composition (y) used in one aspect of the present invention contains a non-adhesive resin, it may further contain an additive for a base material contained in a general base material.
Examples of such an additive for a base material include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent and the like.
These base material additives may be used alone or in combination of two or more.
When these base material additives are contained, the content of each base material additive is preferably 0. With respect to 100 parts by mass of the total amount of the non-adhesive resin contained in the resin composition (y). It is 0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass.

(Organic solvent)
The resin composition (y) used in one aspect of the present invention may be further diluted with an organic solvent to form a solution from the viewpoint of facilitating the formation of a coating film and improving workability.
Examples of the organic solvent include the same ones that can be used in the preparation of the solution of the pressure-sensitive adhesive composition (x).
The organic solvent used in the preparation of the resin composition (y) may be used alone or in combination of two or more.
Further, as the organic solvent used in the preparation of the resin composition (y), the organic solvent used in the synthesis of the resin component may be used as it is, or one or more kinds other than the organic solvent used in the synthesis of the resin component may be used as it is. An organic solvent may be added.

The concentration of the active ingredient of the resin composition (x) used in one embodiment of the present invention is preferably 0.1 to 80% by mass, based on the total amount (100% by mass) of the pressure-sensitive adhesive composition (x). It is preferably 0.5 to 65% by mass, more preferably 1.0 to 50% by mass.

<Release sheet>
The pressure-sensitive adhesive sheet of one aspect of the present invention may further have a release sheet on the surface of the pressure-sensitive adhesive layer.
Examples of the release sheet used in one aspect of the present invention include a sheet having a release agent layer formed from a release agent on one side or both sides of the release sheet base material.

Examples of the base material for the release sheet include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyurethane, and ethylene-. Resin films such as vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer, polystyrene, polycarbonate, fluororesin, low-density polyethylene, linear low-density polyethylene, triacetyl cellulose, high-quality paper, coated paper , Paper base material such as glassin paper, laminated paper in which a thermoplastic resin such as polyethylene is laminated on these paper base materials and the like.

Examples of the release agent forming the release agent layer include silicone-based resins, olefin-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, isoprene-based resins, butadiene-based resins, and other rubber-based elastomers. Be done.

The thickness of the release sheet is not particularly limited, but is preferably 5 to 300 μm, more preferably 7 to 200 μm, and further preferably 10 to 150 μm. When a resin film is used as the base material for the release sheet, the thickness is even more preferably 10 to 100 μm.

[Manufacturing method of adhesive sheet]
The method for producing the pressure-sensitive adhesive sheet according to one aspect of the present invention is not particularly limited. For example, an adhesive sheet having a structure like the adhesive sheet 3 shown in FIG. 1C can be manufactured as follows.
(I) A plurality of layers constituting the resin layer are sequentially formed on the surface of the metal film provided on the base material to form the resin layer, and the formed resin layer is peeled off on the exposed surface. A method of laminating the peeled surfaces of sheets to form an adhesive sheet.
(Ii) A plurality of layers constituting the resin layer are sequentially formed on the peeling surface of the release sheet to form the resin layer, and the formed resin layer is provided on the exposed surface of the base material. A method of laminating the surfaces of the obtained metal films to form an adhesive sheet.
(Iii) A part of the layers constituting the resin layer is formed on the surface of the metal film provided on the base material, and the layer constituting the resin layer is formed on the peeled surface of the release sheet. A method in which the remaining layers are formed and the two formed layers are superposed to form an adhesive sheet.

In the above methods (i) to (iii), it is necessary to form a metal film on the base material in advance.
As a method for forming the metal film, the metal film may be formed by vapor deposition on the base material, or the base material and the metal film may be attached and formed via an adhesive. Further, a commercially available base material with a metal film on which a metal film is formed may be used.

As a method for forming each layer constituting the resin layer, the composition (x) or (y), which is a material for forming each layer, is applied to the surface of the metal film or the peeled surface of the release sheet to form a coating film. Then, the coating film can be dried to form each layer.

Examples of the method for applying the composition (x) or (y) include a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. Can be mentioned.

As the drying conditions of the formed coating film, it is preferable to heat and dry at a temperature of 80 ° C. to 150 ° C. for 30 seconds to 5 minutes (preferably 40 seconds to 3 minutes, more preferably 45 seconds to 2 minutes). ..
When the compositions (x) and (y) contain a cross-linking agent, a seasoning step of holding the composition for a certain period of time (for example, about 1 to 14 days) is performed in order to complete the cross-linking in the formed layer. Is preferable.

In the methods (i) and (ii) above, the plurality of layers forming the resin layer are coated with the compositions which are the respective forming materials to form a coating film at the same time, and the respective coating films are dried at the same time. A resin layer composed of a plurality of layers may be formed. Alternatively, the resin layer may be formed by repeating the steps of applying the composition to the coating film and drying the coating film from the metal film side or the peeling surface side.

For example, as in the adhesive sheet 1a shown in FIG. 2A, the adhesive sheet 1c shown in FIG. 2C, and the adhesive sheet 1f shown in FIG. 2F, the adhesive layer (X) is directly attached to the metal film. In the method for producing a laminated pressure-sensitive adhesive sheet, a pressure-sensitive adhesive composition (x) is applied to the surface of a metal film to form a coating film, and the coating film is dried to form a pressure-sensitive adhesive layer (X). Is preferable.
By directly applying the pressure-sensitive adhesive composition (x) to the metal film in this way to form a coating film, the acrylic in the pressure-sensitive adhesive layer (X) is coated on the surface of the pressure-sensitive adhesive layer on the metal film side. A pressure-sensitive adhesive sheet in which the carboxy group (-COOH) of the polymer (A) is more unevenly distributed can be obtained. As a result, when the obtained pressure-sensitive adhesive sheet is attached to the soda glass, the metal ions that may be generated from the metal oxide contained in the soda glass are transferred to the carboxy group in the pressure-sensitive adhesive layer before being transferred to the metal film. -COOH) can be reacted to suppress the transfer of metal ions to the metal film.

The double-sided adhesive sheet having a structure like the adhesive sheet 2 shown in FIG. 1 (b) and the adhesive sheet 4 shown in FIG. 1 (d) has the above-mentioned (i) to (iii) with respect to one of the metal films. It can be produced by forming a resin layer by a method such as the above, and then forming a resin layer on the other metal film in the same manner.

[Characteristics and applications of adhesive sheets]
The pressure-sensitive adhesive sheet of one aspect of the present invention is suitable for sticking to soda glass, and effectively suppresses so-called "evaporation skipping" in which at least a part of a metal film is oxidized and deteriorated by moisture in the atmosphere. can do.
An adhesive sheet according to one aspect of the present invention is attached to a non-tin surface or a tin surface of a float glass plate conforming to JIS R3202: 2011, and allowed to stand in a high temperature and high humidity environment at 85 ° C. and a relative humidity of 85%. It is preferable that the vapor deposition skipping does not occur even after 96 hours have passed, and more preferably the vapor deposition skipping does not occur even after 168 hours have passed.

The pressure-sensitive adhesive sheet of the present invention is used for sticking to soda glass, but in view of the above-mentioned characteristics of the present invention, it is preferable to use it for sticking soda glass to a non-tin surface.
The use of the adhesive sheet according to one aspect of the present invention is not particularly limited, and for example, it is used as a decorative label or display label attached to the surface of soda glass, a falsification prevention sheet, a conductive sheet for imparting conductivity, and the like. Can be applied to.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Moreover, each physical property value is a value measured by the method shown below.

[Mass average molecular weight (Mw)]
It was measured under the following conditions using a gel permeation chromatograph device (manufactured by Tosoh Corporation, product name "HLC-8020"), and the value measured in terms of standard polystyrene was used.
(Measurement condition)
-Column: "TSK guard volume HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL" and "TSK gel G1000HXL" are connected in sequence (all manufactured by Tosoh Corporation).
-Column temperature: 40 ° C
・ Developing solvent: tetrahydrofuran ・ Flow rate: 1.0 mL / min

[Softening point]
Measured according to JIS K2531.

Production example X-1
(Preparation of Adhesive Composition (x-1))
A pressure-sensitive adhesive composition (x-1) having an active ingredient concentration of 30% by mass was prepared by adding the components and blending amounts shown below and diluting with ethyl acetate.
"Acrylic copolymer (A-i)" (the content ratio of the constituent unit is n-butyl acrylate (BA) / acrylic acid (AAc) = 90.0 / 10.0 (mass%). Polymer, Mw = 470,000): 100 parts by mass (active ingredient ratio)
-"Toluene diisocyanate (TDI)" (product name "Coronate L", manufactured by Tosoh Corporation): 2.0 parts by mass (active ingredient ratio)

Production example X-2
(Preparation of Adhesive Composition (x-2))
A pressure-sensitive adhesive composition (x-2) having an active ingredient concentration of 35% by mass was prepared by adding the components and blending amounts shown below and diluting with ethyl acetate.
-"Acrylic copolymer (A-ii)" (content ratio of constituent units is n-butyl acrylate (BA) / vinyl acetate (VAc) / acrylic acid (AAc) = 90.0 / 5.0 / 5.0 (% by mass) copolymer, Mw = 350,000): 100 parts by mass (active ingredient ratio)
-"Toluene diisocyanate (TDI)" (product name "Coronate L", manufactured by Tosoh Corporation): 1.0 part by mass (active ingredient ratio)

Production example X-3
(Preparation of Adhesive Composition (x-3))
A pressure-sensitive adhesive composition (3) having an active ingredient concentration of 35% by mass was prepared by adding the following components and blending amounts and diluting with ethyl acetate.
"Acrylic copolymer (A-iii)" (content ratio of constituent units is n-butyl acrylate (BA) / 2-ethylhexyl acrylate (2EHA) / acrylic acid (AAc) / 2-hydroxyethyl acrylate ( 2HEA) = 56.0 / 40.0 / 3.5 / 0.5 (mass%) copolymer, Mw = 480,000): 100 parts by mass (active ingredient ratio)
-"Toluene diisocyanate (TDI)" (product name "Coronate L", manufactured by Tosoh Corporation): 1.0 part by mass (active ingredient ratio)

Production example X-4
(Preparation of Adhesive Composition (x-4))
A pressure-sensitive adhesive composition (x-4) having an active ingredient concentration of 40% by mass was prepared by adding the components and blending amounts shown below and diluting with ethyl acetate.
"Acrylic copolymer (A-iv)" (content ratio of constituent units is 2-ethylhexyl acrylate (2EHA) / n-butyl acrylate (BA) / ethyl acrylate (EA) / acrylic acid (AAc) / 2-Hydroxyethyl acrylate (2HEA) = 60.0 / 22.5 / 15.0 / 2.0 / 0.5 (% by mass) copolymer, Mw = 680,000): 100 parts by mass (active ingredient) ratio)
-"Toluene diisocyanate (TDI)" (product name "Coronate L", manufactured by Tosoh Corporation): 0.75 parts by mass (active ingredient ratio)
-"Hydrogen rosin resin" (product name "KE-359", manufactured by Arakawa Chemical Industry Co., Ltd., softening point = 94 to 104 ° C): 25 parts by mass (active ingredient ratio)
-"Aromatic terpene resin" (product name "YS resin TO105", manufactured by Yasuhara Chemical Co., Ltd., softening point = 100 to 110 ° C): 15 parts by mass (active ingredient ratio)

Production example X-5
(Preparation of Adhesive Composition (x-5))
A pressure-sensitive adhesive composition (x-5) having an active ingredient concentration of 30% by mass was prepared by adding the components and blending amounts shown below and diluting with ethyl acetate.
-"Acrylic copolymer (Av)" 2-ethylhexyl acrylate (2EHA) / methyl acrylate (MA) / glycidyl methacrylate (GMA) / acrylic acid (AAc) = 60.0 / 38.0 / 0.5 /1.5 (% by mass) copolymer, Mw = 580,000): 100 parts by mass (active ingredient ratio)
-"Aziridine-based cross-linking agent (Aziridine)" (product name "BXX5134", manufactured by Toyochem Co., Ltd.): 0.24 parts by mass (active ingredient ratio)

Production example Y-1
(Preparation of resin composition (y-1))
A resin composition (y-1), which is also a pressure-sensitive adhesive composition having an active ingredient concentration of 30% by mass, was prepared by adding the components and blending amounts shown below and diluting with ethyl acetate.
-Acrylic copolymer (i) (content ratio of constituent units is n-butyl acrylate (BA) / methyl methacrylate (MMA) / vinyl acetate (VAc) / 2-hydroxyethyl acrylate (2HEA) = 80.0 Copolymer (adhesive resin) of /10.0/9.0/1.0 (mass%), Mw = 600,000): 100 parts by mass (active ingredient ratio)
-"Trimethylolpropane xylene xylene isocyanate (XDI)" (product name "Takenate D-110N", manufactured by Mitsui Chemicals, Inc.): 1.6 parts by mass (active ingredient ratio)
-"Hydrogen rosin resin" (product name "KE-359", manufactured by Arakawa Chemical Industry Co., Ltd., softening point = 94 to 104 ° C): 25 parts by mass (active ingredient ratio)

Production example Y-2
(1) Synthesis of linear urethane prepolymer (Ure) Isophorone diisocyanate is added to 100 parts by mass (active component ratio) of a polycarbonate diol having a mass average molecular weight (Mw) of 1,000 in a reaction vessel under a nitrogen atmosphere. The equivalent ratio of the hydroxyl group of the polycarbonate diol to the isocyanate group of the isophorone diisocyanate is 1/1. Further, 160 parts by mass of toluene is added, and the isocyanate group concentration is theoretically determined while stirring the mixture under a nitrogen atmosphere. The reaction was carried out at 80 ° C. for 6 hours or more until the amount was reached.
Then, a solution obtained by diluting 1.44 parts by mass (active component ratio) of 2-hydroxyethyl methacrylate (HEMA) with 30 parts by mass of toluene was added, and the isocyanate groups at both ends disappeared for another 6 hours at 80 ° C. The reaction was carried out to obtain a linear urethane prepolymer (Ure) having a mass average molecular weight (Mw) of 29000.
(2) Synthesis of acrylic urethane resin (ii) In a reaction vessel under a nitrogen atmosphere, 45.0 parts by mass (active ingredient ratio) of the linear urethane prepolymer (Ure) obtained in (1) above, methyl methacrylate ( MMA) 53.2 parts by mass (active ingredient ratio), 2-hydroxyethyl methacrylate (HEMA) 1.8 parts by mass (active ingredient ratio) and 22.5 parts by mass of toluene were added, and the temperature was raised to 105 ° C. with stirring. bottom. Then, in the reaction vessel, a solution obtained by further diluting 1.0 part by mass (active ingredient ratio) of the radical initiator (manufactured by Nippon Finechem Co., Ltd., product name "ABN-E") with 94.5 parts by mass of toluene was added. The mixture was added dropwise over 4 hours while maintaining the temperature at 105 ° C. After completion of dropping the solution, the reaction was carried out at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin (ii) having a mass average molecular weight (Mw) of 105,000.
(3) Preparation of Resin Composition (y-2) A resin composition (y-) which is also a pressure-sensitive adhesive composition added with the following components and blending amounts, diluted with toluene, and has an active ingredient concentration of 25% by mass. 1) was prepared.
-"Acrylic urethane resin (ii)" (resin obtained through the above (1) and (2), the content ratio of the constituent units is Ure / MMA / HEMA = 45.0 / 53.2 / 1.8 (Mass%) copolymer (adhesive resin), Mw = 105,000): 100 parts by mass (active component ratio)
-"Hexamethylene diisocyanate (HMDI)" (product name "Coronate HL", manufactured by Tosoh Corporation): 2.0 parts by mass (active ingredient ratio)

Examples 1-5
(Making an adhesive sheet)
Polyethylene terephthalate (PET) film with aluminum (Al) vapor deposition film (manufactured by Toray Film Processing Co., Ltd., product name "Metal Me", thickness: 50 μm, by vapor deposition of aluminum film which is a metal film on PET film which is a base material The resin composition (y-1) is applied on the surface of the aluminum-deposited surface of the laminate (thickness formed at 30 to 50 nm) to form a coating film, and the coating film is dried at 100 ° C. for 2 minutes. , A first layer (Y) having a thickness of 5 μm was formed.
Further, the resin composition is placed on the peeling surface of a separately prepared release sheet (manufactured by Lintec Corporation, product name "SP-PET38131", thickness: 38 μm, polyethylene terephthalate (PET) film whose surface has been subjected to silicone peeling treatment). (Y-2) was applied to form a coating film, and the coating film was dried at 110 ° C. for 2 minutes to form a second layer (Y) having a thickness of 5 μm.
Further, any of the pressure-sensitive adhesive compositions (x-1) to (x-5) of the types shown in Table 1 is applied on the peeling-treated surface of the same peeling sheet prepared separately to form a coating film. Then, the coating film was dried at 100 ° C. for 2 minutes to form an adhesive layer (X) having a thickness of 10 μm.
Then, the exposed surface of the first layer (Y) and the exposed surface of the second layer (Y) formed as described above are bonded to each other, and further, the release sheet is removed to create a table. The surface of the second layer (Y) and the surface of the pressure-sensitive adhesive layer (X) were bonded together.
Through the above process, a resin layer having a structure similar to that of the adhesive sheet 1d shown in FIG. 1D (that is, from the Al vapor deposition film side, the first layer (Y) / second layer (Y) / adhesive A pressure-sensitive adhesive sheet having a resin layer (a resin layer formed by sequentially laminating the agent layers (X)) was produced.

Examples 6-10
(Making an adhesive sheet)
The resin composition (y-1) is applied on the surface of the Al-deposited surface of the same PET film with Al-deposited film as used in Example 1 to form a coating film, and the coating film is formed at 100 ° C. It was dried for 2 minutes to form a layer (Y) having a thickness of 10 μm.
In addition, any of the pressure-sensitive adhesive compositions (x-1) to (x-5) of the types shown in Table 1 is placed on the peeled surface of the peeling sheet prepared separately as that used in Example 1 and the like. It was applied to form a coating film, and the coating film was dried at 100 ° C. for 2 minutes to form an adhesive layer (X) having a thickness of 10 μm.
Then, the exposed surface of the layer (Y) and the exposed surface of the pressure-sensitive adhesive layer (X) formed as described above are bonded to each other, and the pressure-sensitive adhesive sheet 1b shown in FIG. 1 (b) has. A pressure-sensitive adhesive sheet having a resin layer having such a structure (that is, a resin layer formed by laminating a layer (Y) / an adhesive layer (X) in this order from the Al-deposited film side) was produced.

Comparative Example 1
(Making an adhesive sheet)
The resin composition (y-1) is applied on the surface of the Al-deposited surface of the same PET film with Al-deposited film as used in Example 1 to form a coating film, and the coating film is formed at 100 ° C. It is dried for 2 minutes to form a layer (Y) having a thickness of 20 μm, and a peel-processed surface of the same release sheet as that used in Example 1 or the like is laminated on the surface of the exposed layer (Y). Then, an adhesive sheet was prepared.

Comparative Example 2
(Making an adhesive sheet)
The resin composition (y-2) is applied on the surface of the Al-deposited surface of the same PET film with Al-deposited film as used in Example 1 to form a coating film, and the coating film is formed at 110 ° C. It is dried for 2 minutes to form a layer (Y) having a thickness of 20 μm, and a peel-processed surface of the same release sheet as that used in Example 1 or the like is laminated on the surface of the exposed layer (Y). Then, an adhesive sheet was prepared.

Using the pressure-sensitive adhesive sheet having the same layer structure as the pressure-sensitive adhesive sheet 3 shown in FIG. 1 (c) produced in Examples and Comparative Examples, the effect of suppressing vapor deposition skipping was evaluated based on the following method. The evaluation results are shown in Table 2.
[Evaluation of the effect of suppressing vapor deposition skipping]
The pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut into squares having a side of 25 mm and used as test samples. The release sheet of the test sample was removed, and the exposed surface of the pressure-sensitive adhesive layer was attached to the non-tin surface or tin surface of a float glass plate conforming to JIS R3202: 2011, at 85 ° C. and a relative humidity of 85. The state of the aluminum film of the test sample after 24 hours, 96 hours, and 168 hours under a high temperature and high humidity environment of% was visually observed through a float glass plate, and vapor deposition was skipped according to the following criteria. The presence or absence was evaluated.
-A: No vapor deposition skipping was observed.
-F: Thin-film deposition skipping was observed.

From Table 2, the pressure-sensitive adhesive sheets prepared in Examples 1 to 10 showed a high effect of suppressing vapor deposition skipping even when left to stand for 168 hours or more in a high-temperature and high-humidity environment. On the other hand, the pressure-sensitive adhesive sheets prepared in Comparative Examples 1 and 2 were left to stand for 96 hours in a high-temperature and high-humidity environment, resulting in thin-film deposition skipping.

1, 1a, 1b, 1c, 1d, 2, 3, 4 Adhesive sheet 10 Base material 20, 20a, 20b Metal film 30, 30a, 30b Resin layer 301, 302, 303, 304, 305, 306 Resin layer (X) Adhesive layer (X)
(Y) Layer (Y)
40, 40a, 40b release sheet

Claims (10)

An adhesive sheet having a base material, a metal film, and a resin layer composed of a plurality of layers laminated on the surface of the metal film.
Acrylic copolymer (A) in which at least one of the plurality of layers constituting the resin layer has a structural unit (a1) derived from an alkyl (meth) acrylate and a structural unit (a2) derived from a carboxy group-containing monomer. A pressure-sensitive adhesive layer (X) formed from the pressure-sensitive adhesive composition (x) containing the above.
Adhesive sheet used for sticking to soda glass. The pressure-sensitive adhesive sheet according to claim 1, wherein the metal film is colored. The pressure-sensitive adhesive sheet according to claim 2, wherein the metal film contains a metal or a metal compound selected from aluminum, chromium, nickel, gold, platinum, silver, tin, copper, iron, palladium, titanium oxide, and titanium nitride. The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the thickness of the resin layer is 1 to 100 μm. The ratio of the thickness of the pressure-sensitive adhesive layer (X) to the thickness of the resin layer [adhesive layer (X) / resin layer] is 0.01 or more, according to any one of claims 1 to 4. The described adhesive sheet. Claims 1 to 5 in which the content of the structural unit (a2) in the pressure-sensitive adhesive composition (x) is 0.1% by mass or more with respect to the total amount of the structural units of the acrylic copolymer (A). The adhesive sheet according to any one of the above. The pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive composition (x) further contains a cross-linking agent (B). The claim that the content of the cross-linking agent (B) in the pressure-sensitive adhesive composition (x) is 0.01 to 20.0 parts by mass with respect to 100 parts by mass of the total amount of the acrylic copolymer (A). The adhesive sheet according to 7. Any of claims 1 to 8, wherein the content of the metal inactivating agent contained in the pressure-sensitive adhesive composition (x) is less than 1 part by mass with respect to 100 parts by mass of the total amount of the acrylic polymer (A). The adhesive sheet described in item 1. The adhesive sheet according to any one of claims 1 to 9, which is used for attaching soda glass to a non-tin surface.

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