JP2020094076A - Adhesive sheet for printing, and manufacturing method of adhesive sheet for printing - Google Patents

Abstract

To provide an adhesive sheet for printing excellent in boundary adhesiveness, printability, falsification prevention, and curve surface followability.SOLUTION: There is provided an adhesive sheet for printing having a laminate by laminating an adhesive layer (X), a substrate layer (Y), and a printing layer (Z) in this order, the laminate is formed by directly laminating a coated film (z') consisting of a composition (z) containing a non-adhesive resin (z1) which is a formation material of the printing layer (Z), and a coated film (y') consisting of a composition (y) containing one or more kind of non-adhesive resin (y1) selected from a group consisting of an acryl urethane resin which is a formation material of the substrate (Y) and an olefin resin in this order, then drying at least the coated films (z') and (y') at same time, in which the adhesive layer (X) is a layer formed from a composition (x) containing an adhesive resin which is a formation material of the adhesive layer (X).SELECTED DRAWING: None

Description

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

A resin base material is mainly used for various printing/printing pressure-sensitive adhesive sheets. Generally, when the base material of the pressure-sensitive adhesive sheet for printing and printing is made of resin, a printing and printing layer is provided on the surface of the base material in order to improve the adhesion to the ink.
Further, it is known that an adhesive layer is provided on the surface of the base material opposite to the printed layer in order to attach the adhesive sheet for printing and printing to an adherend.

For example, in Patent Document 1, a printing tape characterized by being formed of a resin film having elasticity in at least one of a longitudinal direction, a lateral direction, and an oblique direction, and having a rough recording surface. Is disclosed.
Further, in Patent Document 2, a 180° T-type peeling test is made by using an image receiving body in which a release layer and an image receiving layer are sequentially formed on one surface of a sheet-shaped substrate, and an adhesive body having an adhesive layer formed on one surface of a separator. (G/15 mm), the adhesion strength of the base material is 40 to 80 g, and the adhesion strength of the separator is 25 to 39 g.

JP, 2002-120406, A JP, 11-219116, A

By the way, in the conventional printing/printing pressure-sensitive adhesive sheet, there is a problem that the printing ink comes off due to inferior interfacial adhesion between the printing/printing layer and the substrate layer, or when the adherend to be adhered has a curved surface, etc. Problems such as floating and peeling from the body sometimes occurred.
In addition, for example, when the printing and printing pressure-sensitive adhesive sheet is used for a tamper-proof label or the like, for example, when the printing and printing pressure-sensitive adhesive sheet is peeled from the adherend, the base material layer is destroyed to exert the tampering prevention effect. In such a type, there is a possibility that the adherend may be contaminated such that the adhesive or a part of the destroyed base material layer remains on the adherend.

An object of the present invention is to provide a pressure-sensitive adhesive sheet for printing/printing, which is excellent in interfacial adhesion, printing/printing property, tamperproofing property, and curved surface followability.

The present inventors have developed an adhesive layer (X) (hereinafter, also simply referred to as “layer (X)”), a base material layer (Y) (hereinafter, simply referred to as “layer (Y)”), and printing. A pressure-sensitive adhesive sheet for printing and printing, comprising a laminate in which a printing layer (Z) (hereinafter, also simply referred to as "layer (Z)") is laminated in this order, and the laminate is a material for forming the layer (Z). A coating film (z′) formed from a specific composition (z) and a coating film (y′) formed from a specific composition (y) that is a forming material of the layer (Y) in this order. A laminate formed by directly laminating at least the coating film (z') and the coating film (y') at the same time, wherein the pressure-sensitive adhesive layer (X) is formed from the specific composition (x). It has been found that the above problems can be solved by using a pressure-sensitive adhesive sheet for printing and printing as a layer.

That is, the present invention relates to the following [1] to [17].
[1] A pressure-sensitive adhesive sheet for printing/printing, comprising a laminate in which the pressure-sensitive adhesive layer (X), the substrate layer (Y), and the printing/printing layer (Z) are laminated in this order,
The laminate is
A coating film (z′) made of a composition (z) containing a non-adhesive resin (z1) which is a material for forming a print/printing layer (Z);
A coating film (y′) composed of a composition (y) containing one or more non-adhesive resins (y1) selected from the group consisting of acrylic urethane-based resins and olefin-based resins, which are materials for forming the base material layer (Y) )When,
Is directly laminated in this order, and then at least the coating films (z′) and (y′) are simultaneously dried to form a laminate,
A pressure-sensitive adhesive sheet for printing and printing, wherein the pressure-sensitive adhesive layer (X) in the laminate is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin which is a material for forming the pressure-sensitive adhesive layer (X).
[2] The laminate is
The coating film (z'), the coating film (y'), and the coating film (x') composed of the composition (x) are directly laminated in this order, and then the coating film (z') and the coating film (y The adhesive sheet for printing and printing according to [1] above, which is formed by simultaneously drying the coating composition (') and the coating film (x').
[3] The composition (z), the composition (y), and the composition (x) are simultaneously applied to form a coating film (z′), a coating film (y′), and a coating film (x′). And (3) are directly laminated in this order, and then the coating film (z′), the coating film (y′) and the coating film (x′) are simultaneously dried to form the above [2]. Adhesive sheet for printing and printing.
[4] In the above [1] to [3], the thickness ratio of the pressure-sensitive adhesive layer (X) to the total thickness 100 of the base material layer (Y) and the printed print layer (Z) is 20 to 110. The pressure-sensitive adhesive sheet for printing and printing according to any one.
[5] The pressure-sensitive adhesive sheet for printing and printing according to any one of [1] to [4], wherein the laminate has a thickness of 2 to 90 μm.
[6] The pressure-sensitive adhesive sheet for printing and printing according to any of [1] to [5], wherein the base material layer (Y) has a thickness of 0.3 to 50.0 μm.
[7] The pressure-sensitive adhesive sheet for printing and printing according to any of [1] to [6], wherein the pressure-sensitive adhesive resin contained in the composition (x) contains an acrylic resin.
[8] The pressure-sensitive adhesive sheet for printing and printing according to any one of [1] to [7], wherein the non-adhesive resin (y1) is a UV non-curable resin having no polymerizable functional group.
[9] The pressure-sensitive adhesive sheet for printing and printing according to any one of the above [1] to [8], wherein the base material layer (Y) is a non-stretched sheet.
[10] The pressure-sensitive adhesive sheet for printing and printing according to any of [1] to [9], wherein the non-adhesive resin (z1) is a polyester resin and/or a urethane-modified polyester resin.
[11] The pressure-sensitive adhesive sheet for printing and printing according to any of [1] to [10], which has a breaking elongation of 100% or more.
[12] The pressure-sensitive adhesive sheet for printing and printing according to any of [1] to [11], which has a breaking strength of 32 MPa or less.
[13] The pressure-sensitive adhesive sheet for printing and printing according to any one of [1] to [12], which has an elastic modulus of 500 MPa or less.
[14] A method for producing the pressure-sensitive adhesive sheet for printing and printing according to any one of [1] to [13],
A method for producing a pressure-sensitive adhesive sheet for printing and printing, which comprises the following steps (1A) and (2A).
Step (1A): a step of directly laminating a coating film (z') made of the composition (z) and a coating film (y') made of the composition (y) in this order.
-Step (2A): a step of simultaneously drying the coating film (z') and the coating film (y') to form the printed print layer (Z) and the base material layer (Y).
[15] The method for producing a pressure-sensitive adhesive sheet for printing and printing according to [14], which has the following steps (1B) and (2B).
Step (1B): a coating film (z') composed of the composition (z), a coating film (y') composed of the composition (y), and a coating film (x') composed of the composition (x). The process of directly laminating and forming in this order.
Step (2B): a step of drying the coating film (z'), the coating film (y'), and the coating film (x') at the same time to form the laminate.
[16] The method for producing a pressure-sensitive adhesive sheet for printing and printing according to the above [15], wherein in the step (1B), the composition (z), the composition (y), and the composition (x) are simultaneously applied.
[17] The method for producing a pressure-sensitive adhesive sheet for printing and printing according to any of [14] to [16] above, wherein the composition (z) and the composition (y) each independently contain a diluent solvent.

According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet for printing/printing, which is excellent in interfacial adhesion, printing/printing property, tampering prevention property, and curved surface followability.

It is a cross-sectional schematic diagram of the adhesive sheet for printing and printing which shows an example of a structure of the adhesive sheet for printing and printing of this invention.

In the present invention, the judgment of whether the target resin belongs to the “adhesive resin” or the “non-adhesive resin” is made based on the following procedures (1) to (4).
-Procedure (1): A 20 μm-thick resin layer formed only from the target resin was provided on a 50 μm-thick polyethylene terephthalate (PET) film, and a test piece cut into a size of 300 mm length×25 mm width was used. Create.
-Procedure (2): Under the environment of 23° C. and 50% RH (relative humidity), the surface of the resin layer of the test piece on the exposed side is attached to a stainless plate (SUS304 No. 360 polishing), and the same. Let stand for 24 hours in the environment.
-Procedure (3): After standing, in an environment of 23° C. and 50% RH (relative humidity), based on JIS Z0237:2000, a 180° peeling method and an adhesive force at a pulling speed of 300 mm/min. taking measurement.
-Procedure (4): If the measured adhesive force is 0.1 N/25 mm or more, the target resin is determined to be "adhesive resin". On the other hand, if the measured adhesive force is less than 0.1 N/25 mm, the target resin is determined to be “non-adhesive resin”.

In the present invention, the “active ingredient” refers to the ingredient contained in the target composition excluding the diluent solvent.
Further, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are standard polystyrene conversion values measured by a gel permeation chromatography (GPC) method, and specifically, based on the method described in Examples. It is the value measured by

In the present invention, for example, “(meth)acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and other similar terms are also the same.
Regarding the preferable numerical value range (for example, the range of the content or the like), the lower limit value and the upper limit value described stepwise can be independently combined. For example, from the description "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". You can also Similarly, for example, from the description "preferably 10 or more, more preferably 30 or more, and preferably 90 or less, more preferably 60 or less", "10 or more and 60 or less" as a suitable range It is possible to select, or it is possible to simply select the range of "60 or less".

[Adhesive sheet for printing and printing]
The pressure-sensitive adhesive sheet for printing/printing of the present invention is a pressure-sensitive adhesive sheet for printing/printing having a laminate in which the pressure-sensitive adhesive layer (X), the substrate layer (Y), and the printing/printing layer (Z) are laminated in this order, The laminate comprises a coating film (z') made of a composition (z) containing a non-adhesive resin (z1) which is a material for forming a printing/printing layer (Z), and a material for forming a base material layer (Y). A coating film (y') made of a composition (y) containing one or more non-adhesive resin (y1) selected from the group consisting of an acrylic urethane resin and an olefin resin was directly laminated in this order. After that, at least the coating films (z′) and (y′) are simultaneously dried to form a laminate, and the adhesive layer (X) in the laminate is a material for forming the adhesive layer (X). A pressure-sensitive adhesive sheet for printing and printing, which is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin.

FIG. 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet for printing and printing showing an example of the constitution of the pressure-sensitive adhesive sheet for printing and printing of the present invention.
For example, the pressure-sensitive adhesive sheet for printing/printing of the present invention is the same as the pressure-sensitive adhesive sheet for printing/printing 1 shown in FIG. 1( a), the pressure-sensitive adhesive layer (X) 12, the base material layer (Y) 11, and the printing/printing layer ( Examples of the laminate 10 include a laminate 10 in which Z) 13 is laminated in this order. In the laminate 10, at least the base material layer (Y) 11 and the print layer (Z) 13 are directly laminated in this order. In the pressure-sensitive adhesive sheet for printing and printing of the present invention, it is preferable that the pressure-sensitive adhesive layer (X), the base material layer (Y) and the printing and printing layer (Z) are directly laminated in this order.
Here, the above-mentioned “direct lamination” means, for example, in the former case, the two layers are in direct contact with each other without any other layer between the base material layer (Y) and the printing and printing layer (Z). In the case of the latter, the other between the pressure-sensitive adhesive layer (X) and the base material layer (Y) and between the base material layer (Y) and the print/printing layer (Z). It means that the pressure-sensitive adhesive layer (X) and the print layer (Z) are directly in contact with the base material layer (Y) independently of each other without any layer.
Further, the release material described below is not included in the constitution of the “laminate” included in the pressure-sensitive adhesive sheet for printing and printing of the present invention.

The pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention may be configured to further include a release material on the surface of the pressure-sensitive adhesive layer (X) from the viewpoint of handleability.
For example, as the pressure-sensitive adhesive sheet for printing/printing of the aspect, as shown in FIG. 1B, the pressure-sensitive adhesive sheet for printing/printing 2 further having a release material 141 on the surface of the pressure-sensitive adhesive layer (X) 12 can be mentioned. ..

Moreover, as the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention, a different forming material is provided on the sticking surface of the pressure-sensitive adhesive layer (X) (on the surface opposite to the side in contact with the base material layer). The adhesive layer (X′) formed from the composition may be laminated (not shown).
The pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is an intermediate layer (M) formed from a composition which is a different forming material between the base material layer (Y) and the pressure-sensitive adhesive layer (X). (For example, a primer layer) may be laminated (not shown).
That is, the pressure-sensitive adhesive sheet for printing and printing, which is one aspect of the present invention, is not limited to the sheet of each aspect shown in FIG. 1 as long as the above-mentioned aspect is satisfied.

<Laminate>
The laminate of the pressure-sensitive adhesive sheet for printing and printing of the present invention is a laminate in which the pressure-sensitive adhesive layer (X), the base material layer (Y), and the printing and printing layer (Z) are laminated in this order. A coating film (z') made of a composition (z) containing a non-adhesive resin (z1) that is a forming material of Z), and an acrylic urethane resin and an olefin resin that is a forming material of the base material layer (Y). After directly laminating a coating film (y') comprising a composition (y) containing at least one non-adhesive resin (y1) selected from the group consisting of at least a coating film (z') And (y′) are simultaneously dried, and the pressure-sensitive adhesive layer (X) in the laminate is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin.
The pressure-sensitive adhesive layer (X) is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin, and may be, for example, one that is melted by heating and extrusion-laminated on the base material layer (Y). Alternatively, a coating film (x′) composed of the composition (x) containing an adhesive resin may be formed by coating the base material layer (Y) afterwards and drying. In addition, for example, the pressure-sensitive adhesive layer (X) is a product obtained by previously extruding or drying the coating film (x′) and then pasting it onto the base material layer (Y) directly or through another layer. May be The pressure-sensitive adhesive layer (X) is preferably a layer formed by drying a coating film (x′) composed of the composition (x), and more preferably a coating film (z′) and a coating film (y). ') and dried at the same time.
And more preferably, as the laminate, after directly laminating a coating film (z′), a coating film (y′), and a coating film (x′) composed of the composition (x) in this order. The coating film (z'), the coating film (y') and the coating film (x') are simultaneously dried.

Even more preferably, as the laminate, at least the composition (z) and the composition (y) are simultaneously applied to form a coating film (z′), a coating film (y′), and a composition ( and a coating film (x′) consisting of x) are directly laminated in this order, and then the coating film (z′), the coating film (y′) and the coating film (x′) are simultaneously dried. is there. By applying the composition (z) and the composition (y) at the same time, a thin dry film is less likely to be formed on the surface of the coating film as compared with the case of sequentially applying each composition, and thus the obtained printing Excellent adhesion between the print layer (Z) and the base material layer (Y).
From the same viewpoint, more preferably, as the laminate, the composition (z), the composition (y), and the composition (x) are simultaneously applied to form a coating film (z′), The coating film (y') and the coating film (x') are directly laminated in this order, and then the coating film (z'), the coating film (y') and the coating film (x') are dried at the same time. It was done. By applying the composition (z), the composition (y), and the composition (x) at the same time, a thin dry film is formed on each coating surface as compared with the case where each composition is sequentially applied. Since it is less likely to occur, the adhesiveness between the obtained layers is excellent.

Conventionally, a pressure-sensitive adhesive sheet for printing and printing is manufactured, for example, by the following method (hereinafter, also referred to as “conventional manufacturing method”).
-Preparing a coating film formed by applying a pressure-sensitive adhesive composition on the release-treated surface of a release material such as a release film, and drying the coating film to form a pressure-sensitive adhesive layer. On the release-treated surface of the release material, a composition for forming a print/printing layer is applied to form a coating film, and the coating film is dried to prepare a print/printing layer-formed base film or A manufacturing method comprising a step of attaching a pressure-sensitive adhesive layer and a printed layer formed on a release material to the front and back surfaces of a base material layer such as a sheet.
In the above-mentioned conventional manufacturing method, the base material layer formed in advance is used, and the pressure-sensitive adhesive layer and the print printing layer are formed in advance on the release-treated surface of the release film.
However, the pressure-sensitive adhesive sheet for printing and printing with a substrate obtained by the above-mentioned conventional manufacturing method, since the substrate layer and the printing and printing layer are formed separately, the substrate layer and the printing and printing layer. Interface adhesion is low.

On the other hand, the laminate of the pressure-sensitive adhesive sheet for printing and printing of the present invention comprises a coating film (y′) composed of the composition (y) which is a material for forming the base material layer (Y) and a printing and printing layer (Z). A coating film (z') composed of the composition (z) which is a forming material is directly laminated in this order, and then at least the coating film (y') and the coating film (z') are dried "at the same time" to be formed. It was done.
Since the laminate is formed in this way, the interfacial adhesion between the base material layer (Y) and the print/printing layer (Z) is higher than that of the pressure-sensitive adhesive sheet for print/printing obtained by the above-mentioned general manufacturing method. Will be things.
This is a coating film (y') made of the composition (y) that is a material for forming the base layer (Y) and a coating film (z) that is a composition (z) that is a material for forming the printing and printing layer (Z). z') is simultaneously dried, a mixed layer of the coating film is formed near the interface, and the molecular chains of the resins contained in the respective compositions are entangled with each other, so that the base layer (Y) and the print-printed layer (Z It is thought that this is because the interfacial adhesiveness with
Furthermore, the base material layer (Y) of the pressure-sensitive adhesive sheet for printing and printing of the present invention is formed by drying the coating film (y′) composed of the composition (y), as described above. Unlike the base film or sheet used in the conventional manufacturing method, it is a non-stretched sheet. Therefore, the pressure-sensitive adhesive sheet for printing/printing of the present invention is remarkably excellent in flexibility as compared with the pressure-sensitive adhesive sheet for printing/printing obtained by the conventional manufacturing method.

In the present specification, the term “non-stretched sheet material” excludes a sheet material obtained by intentionally stretching in a specific direction. For example, in a continuous manufacturing process using a roll to roll manufacturing apparatus or the like, when stretched in the flow direction due to force applied unavoidably, it is not limited to that, and may be regarded as "non-stretched sheet-like material". it can.
As a result, the pressure-sensitive adhesive sheet for printing and printing of the present invention is excellent in curved surface followability.

Similarly, in the laminate, the coating film (z′), the coating film (y′), and the coating film (x′) composed of the composition (x) are directly laminated in this order and then coated. When formed by simultaneously drying the film (z'), the coating film (y') and the coating film (x'), the interfacial adhesion between the substrate layer (Y) and the print-printing layer (Z) Not only that, the interfacial adhesion between the pressure-sensitive adhesive layer (X) and the base material layer (Y) is higher than that of the pressure-sensitive adhesive sheet for printing and printing obtained by the above-mentioned conventional manufacturing method.
For the same reason as described above, this is a coating film (y′) made of the composition (y) that is a material for forming the base material layer (Y), and a composition (a composition that is a material for forming the adhesive layer (X) ( In the process of simultaneously drying the coating film (x′) composed of x), the molecular chains of the adhesive resin and the non-adhesive resin (y1) contained in the composition of each other, while forming a mixed layer of the coating film near the interface. It is thought that the interfacial adhesion between the base material layer (Y) and the pressure-sensitive adhesive layer (X) is improved due to the entanglement with the molecular chain of.

In the present invention, the laminated body of the pressure-sensitive adhesive sheet for printing and printing is specified by the manufacturing method as described above, but there is a unavoidable situation in which the manufacturing method has to be specified.
That is, the cross section in the thickness direction obtained by cutting the laminate in the direction perpendicular to the surface of the print-printing layer (Z) is examined by using an electron microscope or the like to determine the interface between the base layer (Y) and the print-printing layer (Z). As a method of determining whether or not the film is formed based on the method of the present invention from the viewpoint of subjective visual observation by observing, the method of measuring the surface roughness can be considered, for example. However, since the roughness of the interface is very small, it cannot be accurately measured, and the difference in the roughness state depending on the observed region is very large. Therefore, it is extremely difficult to evaluate using specific physical property values such as surface roughness.
Under such circumstances, in the present invention, the laminate included in the pressure-sensitive adhesive sheet for printing and printing is specified by the manufacturing method as described above.
After the laminated body directly laminates the coating film (z'), the coating film (y') and the coating film (x') in this order, the coating film (z') and the coating film (y'). And the relationship between the base material layer (Y) and the printed printing layer (Z), and the base material layer (Y) and the pressure-sensitive adhesive layer, in the case of being formed by simultaneously drying the coating film (x′) The same applies to the relationship with (X).

In the present specification, the “coating film” is a film formed from a composition as a forming material by a known coating method, and the residual ratio of volatile components such as a solvent contained in the film is The total amount of volatile components contained in the composition before coating is 100% by mass, and 10 to 100% by mass.
That is, in the present specification, the coating film (x′), the coating film (y′), and the coating film (z′) contain a certain amount of a volatile component such as a solvent.
And the said laminated body removes a volatile component by drying at least a coating film (y') and a coating film (z') simultaneously, and has a base material layer (Y) and a printing print layer (Z). The body is formed. In the case of the preferable laminate described above, the volatile component is removed by simultaneously drying the three coating films of the coating film (x'), the coating film (y'), and the coating film (z'), and the adhesion is improved. A laminate composed of the agent layer (X), the base material layer (Y), and the printing/printing layer (Z) is formed.

The method for forming the coating film (x'), the coating film (y'), and the coating film (z'), and the drying conditions for the formed coating film are described in "Printing and Printing Adhesive Sheet Manufacturing method” is as described in the item.

<<Adhesive Layer (X)>>
The pressure-sensitive adhesive layer (X) is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin.
As described above, the pressure-sensitive adhesive layer (X) may be a layer formed of the composition (x) containing the pressure-sensitive adhesive resin, but the coating film (x′) formed of the composition (x) is preferably dried. It is a layer formed by doing so, and more preferably, it is formed by drying simultaneously with the coating film (z′) and the coating film (y′).

[Composition (x)]
The composition (x), which is a material for forming the adhesive layer (X), contains an adhesive resin.
In addition, in one aspect of the present invention, the components other than the adhesive resin contained in the composition (x) can be appropriately adjusted according to the intended use of the adhesive sheet for printing and printing of the present invention.
For example, in one aspect of the present invention, the composition (x) may further contain a tackifier and/or a cross-linking agent, from the viewpoint of a pressure-sensitive adhesive sheet for printing and printing with further improved adhesive strength. Besides, it may contain a diluent solvent and/or an additive for a pressure-sensitive adhesive used for a general pressure-sensitive adhesive.

(Adhesive resin)
The mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, and further preferably 30,000 to 1,000,000 from the viewpoint of improving the adhesive strength.
Examples of the adhesive resin contained in the composition (x) include an acrylic resin, a urethane resin, a polyisobutylene resin, and an olefin resin that satisfy the adhesive strength of the adhesive resin.
These adhesive resins may be used alone or in combination of two or more.
Further, when these adhesive resins are copolymers having two or more kinds of constitutional units, the form of the copolymer is not particularly limited, and the block copolymer, the random copolymer, and the graft copolymer may be used. It may be any of polymers.
Further, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y) and the pressure-sensitive adhesive layer (X), these pressure-sensitive adhesive resins are UV non-curable pressure-sensitive adhesive resins having no polymerizable functional group. Preferably there is.

The content of the adhesive resin in the composition (x) is preferably 30 to 99.99% by mass, more preferably 40 to 99% with respect to the total amount (100% by mass) of the active ingredients of the composition (x). The content is preferably 0.95% by mass, more preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, still more preferably 60 to 99.50% by mass.

{Acrylic resin}
In one aspect of the present invention, the adhesive resin contained in the composition (x) preferably contains an acrylic resin from the viewpoint of further improving the interfacial adhesion with the base material layer (Y).
The content ratio of the acrylic resin in the adhesive resin is preferably 30 to 30 with respect to the total amount (100% by mass) of the adhesive resin contained in the composition (x), from the viewpoint of further improving the interfacial adhesion. The amount is 100% by mass, more preferably 50 to 100% by mass, further preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.

As the acrylic resin that can be used as the adhesive resin, for example, a polymer containing a structural unit derived from an alkyl (meth)acrylate having a linear or branched alkyl group, or a (meth)acrylate having a cyclic structure can be used. Examples thereof include polymers containing a constituent unit derived from them.

The mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. ..

The acrylic resin used in one embodiment of the present invention includes an acrylic polymer having a structural unit (a1) derived from an alkyl(meth)acrylate (a1′) (hereinafter, also referred to as “monomer (a1′)”). (A0) is preferable, and the acrylic copolymer has the structural unit (a1) and the structural unit (a2) derived from the functional group-containing monomer (a2′) (hereinafter, also referred to as “monomer (a2′)”). (A1) is more preferable.

The number of carbon atoms of the alkyl group contained in the monomer (a1′) is preferably 1 to 24, more preferably 1 to 12, further preferably 1 to 8, and even more preferably 4 to 6 from the viewpoint of improving the adhesive property. Is.
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, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl ( Examples thereof include (meth)acrylate and stearyl (meth)acrylate.
These monomers (a1′) may be used alone or in combination of two or more kinds.
As the monomer (a1′), methyl(meth)acrylate, butyl(meth)acrylate and 2-ethylhexyl(meth)acrylate are preferable, and methyl(meth)acrylate and butyl(meth)acrylate are more preferable.

The content of the structural unit (a1) is preferably 50 to 100% by mass, more preferably 100% by mass based on all structural units (100% by mass) of the acrylic polymer (A0) or the acrylic copolymer (A1). The content is 60 to 99.9% by mass, more preferably 70 to 99.5% by mass, and still more preferably 80 to 99.0% by mass.

The functional group contained in the monomer (a2′) refers to a functional group capable of acting as a starting point of crosslinking or a functional group having a crosslinking promoting effect by reacting with a crosslinking agent which may be contained in the composition (x) described later. , Carboxy group, amino group, epoxy group and the like.
That is, examples of the monomer (a2′) include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
These monomers (a2′) may be used alone or in combination of two or more kinds.
As the monomer (a2′), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth). ) Hydroxyalkyl (meth)acrylates such as acrylate and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.

Examples of the carboxy group-containing monomer 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, and anhydrides thereof. 2-(acryloyloxy)ethyl succinate, 2-carboxyethyl(meth)acrylate and the like can be mentioned.
As the monomer (a2′), 2-hydroxyethyl(meth)acrylate is preferable.

The content of the structural unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.3 to 30% with respect to the total structural units (100% by mass) of the acrylic copolymer (A1). %, more preferably 0.5 to 20% by mass, still more preferably 0.7 to 10% by mass.

The acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3′) other than the monomers (a1′) and (a2′).
In the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is preferably 70 based on the total structural units (100 mass%) of the acrylic copolymer (A1). To 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.

Examples of the monomer (a3′) include olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene-based monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth)acrylate, Has a cyclic structure such as benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, imide (meth)acrylate (Meth)acrylate; styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth)acrylamide, (meth)acrylonitrile, (meth)acryloylmorpholine, N-vinylpyrrolidone and the like.
Vinyl acetate is preferred as the monomer (a3′).

{Urethane resin}
The urethane resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of the main chain and the side chain.
Specific urethane-based resins include, for example, urethane-based prepolymers (UX) obtained by reacting a polyol with a polyvalent isocyanate compound.
The urethane prepolymer (UX) may be obtained by further subjecting a chain extension reaction using a chain extender.

The mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, still more preferably 20,000 to. It is 70,000.

Examples of the polyol that is a raw material of the urethane-based prepolymer (UX) include polyol compounds such as alkylene type polyol, polyether type polyol, polyester type polyol, polyesteramide type polyol, polyester/polyether type polyol, and polycarbonate type polyol. However, the polyol is not particularly limited as long as it is a polyol, and may be a bifunctional diol or a trifunctional triol.
These polyols may be used alone or in combination of two or more.
Among these polyols, diols are preferable, and alkylene type diols are more preferable, from the viewpoints of easy availability, reactivity, and the like.

Examples of the alkylene type diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol; ethylene glycol, propylene glycol, Examples thereof include alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; and polyoxyalkylene glycols such as polytetramethylene glycol.
Among these alkylene type diols, glycols having a mass average molecular weight (Mw) of 1,000 to 3,000 are preferable from the viewpoint of suppressing gelation when further reacting with a chain extender.

Examples of the polyisocyanate compound as a raw material of the urethane prepolymer (UX) include aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like.
Examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), and 2 ,6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′ -Diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples thereof include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI:isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanate Methyl) cyclohexane and the like.
The polyisocyanate compound may be a trimethylolpropane adduct type modified product of the above polyisocyanate, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.

Among these polyvalent isocyanate compounds, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, from the viewpoint of obtaining a urethane polymer having excellent adhesive properties. One or more selected from 6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, one or more selected from HMDI, IPDI and modified products thereof are more preferable.

The isocyanate group content (NCO%) in the urethane prepolymer (UX) is preferably 0.5 to 12% by mass, more preferably 1 to 4 in the value measured according to JIS K1603-1:2007. It is% by mass.

As the chain extender, a compound having at least two hydroxyl groups and/or amino groups, or a compound having at least three hydroxyl groups and/or amino groups is preferable.

The compound having at least two of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of an aliphatic diol, an aliphatic diamine, an alkanolamine, a bisphenol and an aromatic diamine.
Examples of the aliphatic diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol. Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; and the like.
Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine and the like.
Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
Examples of the bisphenol include bisphenol A and the like.
Examples of aromatic diamines include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.

Examples of the compound having at least one of three or more hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; 1-amino-2,3-propanediol, 1-methyl. And amino alcohols such as amino-2,3-propanediol and N-(2-hydroxypropylethanolamine); ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine; and the like.

{Polyisobutylene resin}
The polyisobutylene-based resin (hereinafter, also referred to as “PIB-based resin”) that can be used as the adhesive resin is not particularly limited as long as it is a resin having a polyisobutylene skeleton in at least one of the main chain and the side chain.

The mass average molecular weight (Mw) of the PIB-based resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, further preferably 50,000 to 800,000, still more preferably 70,000 to 600,000.

Examples of the PIB-based resin include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and copolymers thereof. Examples thereof include brominated or chlorinated halogenated butyl rubber and the like.

When the PIB-based resin is a copolymer, it is assumed that the structural unit composed of isobutylene is contained in the largest amount among all the structural units.
The content of the constitutional unit composed of isobutylene is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and further preferably 95 to 100% by mass based on the total constitutional units (100% by mass) of the PIB resin. %.
These PIB-based resins may be used alone or in combination of two or more.

When using a PIB-based resin, it is preferable to use a PIB-based resin having a high mass average molecular weight (Mw) and a PIB-based resin having a low mass average molecular weight (Mw) together.
More specifically, a PIB resin (p1) having a mass average molecular weight (Mw) of 270,000 to 600,000 (hereinafter, also referred to as "PIB resin (p1)") and a mass average molecular weight (Mw) of 5 are used. It is preferable to use in combination with 10,000 to 250,000 PIB-based resins (p2) (hereinafter, also referred to as “PIB-based resins (p2)”).
By using the PIB-based resin (p1) having a high mass average molecular weight (Mw), it is possible to improve the durability and weather resistance of the pressure-sensitive adhesive layer to be formed and also improve the pressure-sensitive adhesive force.
Further, by using the PIB-based resin (p2) having a low mass average molecular weight (Mw), the PIB-based resin (p1) can be suitably compatible with each other and the PIB-based resin (p1) can be appropriately plasticized. The wettability of the pressure-sensitive adhesive layer with respect to the adherend can be improved, and the adhesive physical properties, flexibility and the like can be improved.

The mass average molecular weight (Mw) of the PIB-based resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, further preferably 310,000 to 450,000, still more preferably 320,000 to 400,000. Is.
The mass average molecular weight (Mw) of the PIB resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, still more preferably 180,000 to 210,000. Is.

The content ratio of the PIB resin (p2) to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and still more It is preferably 8 to 20 parts by mass.

{Olefin resin}
The olefin resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
The olefin resin may be used alone or in combination of two or more kinds.
Specific olefin resins include, for example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other α-. Copolymer with olefin, Copolymer with propylene and other α-olefin, Copolymer with ethylene and propylene and other α-olefin, Copolymer with ethylene and other ethylenically unsaturated monomer Examples thereof include polymers (ethylene-vinyl acetate copolymer, ethylene-alkyl(meth)acrylate copolymer, etc.).
Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
Examples of the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth)acrylate, vinyl alcohol and the like.

(Tackifier)
In one aspect of the present invention, it is preferable that the composition (x) further contains a tackifier, from the viewpoint of a pressure-sensitive adhesive sheet for printing and printing with improved adhesive strength.
Here, the "tackifier" is a component that secondarily improves the adhesive strength of the adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, and the adhesive resin described above. It is a distinction.
The mass average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and further preferably 800 to 5,000.

Examples of the tackifier include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, aromatic modified terpene resins, terpene phenols. -Based resins and other terpene-based resins; hydrogenated terpene-based resins obtained by hydrogenating these terpene-based resins; styrene obtained by copolymerizing styrene-based monomers such as α-methylstyrene or β-methylstyrene with aliphatic monomers -Based resins; hydrogenated styrene-based resins obtained by hydrogenating these styrene-based resins; C5-based resins obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1.3-pentadiene produced by thermal decomposition of petroleum naphtha Petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; C9 petroleum resin obtained by copolymerizing C9 fractions such as indene and vinyltoluene produced by thermal decomposition of petroleum naphtha, and hydrogen of this C9 petroleum resin Chemical petroleum resin; and the like.
These tackifiers may be used alone or in combination of two or more having different softening points and structures.

The softening point of the tackifier is preferably 60 to 170°C, more preferably 65 to 160°C, and further preferably 70 to 150°C.
In addition, in this specification, the "softening point" of a tackifier means the value measured based on JISK2531.
When two or more tackifiers are used, the weighted average of the softening points of the tackifiers preferably falls within the above range.

The content of the tackifier in the composition (x) is preferably 0.01 to 65% by mass, more preferably 0.1% by mass based on the total amount (100% by mass) of the active ingredients in the composition (x). 05 to 55% by mass, more preferably 0.1 to 50% by mass, even more preferably 0.5 to 45% by mass, still more preferably 1.0 to 40% by mass.

The total content of the tackifying resin and the tackifier in the composition (x) is preferably 70% by mass or more, more preferably 100% by mass based on the total amount (100% by mass) of the active ingredients of the composition (x). Is 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more.

(Crosslinking agent)
In one embodiment of the present invention, the composition (x) further contains a cross-linking agent together with the adhesive resin having the above-mentioned functional group such as the acrylic copolymer having the above-mentioned constitutional units (a1) and (a2). Preferably.
The crosslinking agent reacts with a functional group of the adhesive resin to crosslink the resins with each other.

Examples of the cross-linking agent include isocyanate cross-linking agents such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and adducts thereof; epoxy cross-linking agents such as ethylene glycol glycidyl ether; hexa[1-(2- Methyl)-aziridinyl]triphosphatriazine and other aziridine crosslinking agents; aluminum chelate and other chelating crosslinking agents; and the like.
These crosslinking agents may be used alone or in combination of two or more kinds. Among these cross-linking agents, the isocyanate cross-linking agent is preferable from the viewpoint of enhancing cohesive force to improve the adhesive force, and availability and the like.

The content of the cross-linking agent is appropriately adjusted depending on the number of functional groups contained in the adhesive resin, and for example, with respect to 100 parts by mass of the adhesive resin having the above-mentioned functional group such as the acrylic copolymer. It is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, still more preferably 0.05 to 4 parts by mass.

(Adhesive additive)
In one aspect of the present invention, the composition (x) contains an additive for a pressure-sensitive adhesive used for general pressure-sensitive adhesives other than the above-mentioned tackifier and cross-linking agent, within a range that does not impair the effects of the present invention. You may have.
Examples of the adhesive additive include an antioxidant, a softening agent (plasticizer), an antirust agent, a pigment, a dye, a retarder, a catalyst, an ultraviolet absorber, and the like.
These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
When these additives for pressure-sensitive adhesives are contained, the content of each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 100 parts by mass of the adhesive resin. It is 0.001 to 10 parts by mass.

(Diluting solvent)
In one aspect of the present invention, the composition (x) may be in the form of a solution containing water or an organic solvent as a diluting solvent together with the above-mentioned various active ingredients.
Examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, tert-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, cyclohexane. Etc.
In addition, these diluent solvents may be used alone or in combination of two or more kinds.

When the composition (x) contains a diluent solvent and is in the form of a solution, the concentration of the active ingredient of the composition (x) is preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass. %, and more preferably 1.0 to 45 mass %.

<<Base material layer (Y)>>
The base material layer (Y) is formed by drying a coating film (y′) composed of a composition (y) containing one or more non-adhesive resins (y1) selected from the group consisting of acrylic urethane resins and olefin resins. The layer is formed by being dried, and is formed by drying simultaneously with the coating film (z′) made of the composition (z) described later.

[Composition (y)]
The composition (y), which is a material for forming the base material layer (Y), contains at least one non-adhesive resin (y1) selected from the group consisting of an acrylic urethane resin and an olefin resin.
In addition, in 1 aspect of this invention, components other than the non-adhesive resin (y1) contained in a composition (y) can be suitably adjusted according to the use use of the adhesive sheet for printing and printing of this invention.
For example, in one aspect of the present invention, the composition (y) may contain a resin other than an acrylic urethane resin and an olefin resin as long as the effect of the present invention is not impaired, and a diluting solvent and/or Or you may contain the additive for base materials contained in the base material which a general adhesive sheet has.

(Non-adhesive resin (y1))
The non-adhesive resin (y1) belongs to an acrylic urethane resin or an olefin resin.
When the non-adhesive resin (y1) is a copolymer having two or more constitutional units, the form of the copolymer is not particularly limited, and the block copolymer, the random copolymer, and the graft copolymer may be used. It may be any of polymers.
Further, in one aspect of the present invention, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y) and the printing/printing layer (Z) and the pressure-sensitive adhesive layer (X), the composition is contained in the composition (y). The non-adhesive resin (y1) is preferably an ultraviolet non-curable resin having no polymerizable functional group.

The content of the non-adhesive resin (y1) in the composition (y) is preferably 50 to 100% by mass, more preferably 65% by mass based on the total amount (100% by mass) of the active ingredients of the composition (y). To 100% by mass, more preferably 80 to 98% by mass, still more preferably 90 to 96% by mass.

{Acrylic urethane resin}
Examples of the acrylic urethane-based resin contained as the non-adhesive resin (y1) in the composition (y) include, for example, a reaction product of an acrylic polyol compound and an isocyanate compound, and a direct product having an ethylenically unsaturated group at both ends. Examples thereof include a copolymer obtained by polymerizing a chain urethane prepolymer (UY) and a vinyl compound (VY) containing a (meth)acrylic acid ester.

The acrylic urethane-based resin (hereinafter, also referred to as “acrylic urethane-based resin (I)”), which is a reaction product of an acrylic polyol compound and an isocyanate compound, has a main chain of an acrylic-based resin as a skeleton and has an intermolecular structure between them. Has a chemical structure that is cured by being crosslinked by a urethane bond.
Since the acrylic resin, which is the main chain, is highly rigid, it can withstand tensile stress and is difficult to stretch, and since it has a structural unit derived from a highly reactive isocyanate compound, it is not included in the printing and printing layer (Z). It is considered that since it has excellent adhesiveness with the adhesive resin (z1), it can contribute to improvement of interfacial adhesiveness with the layer (Z). Furthermore, since the adhesiveness to the adhesive resin contained in the pressure-sensitive adhesive layer (X) is also excellent, it is considered that it can contribute to the improvement of the interfacial adhesion to the adhesive layer (X).

On the other hand, an acrylic urethane-based resin which is a copolymer obtained by polymerizing a linear urethane prepolymer (UY) having an ethylenically unsaturated group at both ends and a vinyl compound (VY) containing a (meth)acrylic acid ester ( Hereinafter, also referred to as "acrylic urethane-based resin (II)") has a main chain of a linear urethane prepolymer (UY) as a skeleton and (meth)acrylic acid at both ends of the linear urethane prepolymer (UY). It has a structural unit derived from a vinyl compound (VY) containing an ester.
In the acrylic urethane-based resin (II), since the site derived from the linear urethane polymer (UY) is interposed between the acrylic sites in the main chain skeleton, the distance between crosslinking points becomes longer than that of the acrylic urethane-based resin (I). , Its molecular structure tends to be a two-dimensional structure (mesh structure).
Further, since the urethane prepolymer (UY) of the main chain is linear, the stretching effect is high when an external force is applied.
Further, the side chain of the structural unit derived from the vinyl compound (VY) containing the (meth)acrylic acid ester has a non-adhesive resin (z1) in the printing and printing layer (Z) and an adhesive in the adhesive layer (X). It has a structure that is easily entangled with the resin.
Therefore, by using an acrylic urethane-based resin (II) as a material for forming the base material layer (Y), it is possible to improve the interfacial adhesion with the print layer (Z) and further to improve the adhesiveness with the adhesive layer (X). It is considered that it can contribute to the improvement of interfacial adhesion.

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, still more preferably 10,000 to It is 150,000.

In one aspect of the present invention, the acrylic urethane-based resin (II) is preferable as the acrylic urethane-based resin contained in the composition (y) as the non-adhesive resin (y1).
The acrylic urethane resins (I) and (II) will be described below.

{{Acrylic urethane resin (I)}}
The acrylic polyol compound, which is a raw material of the acrylic urethane resin (I), is a structural unit (b1) derived from an alkyl (meth)acrylate (b1′) (hereinafter, also referred to as “monomer (b1′)”). An acrylic copolymer (B1) having a structural unit (b2) derived from a hydroxyl group-containing monomer (b2′) (hereinafter, also referred to as “monomer (b2′)”) is preferable.

The carbon number of the alkyl group contained in the monomer (b1′) is preferably 1 to 12, more preferably 4 to 8, and further preferably 4 to 6.
The alkyl group contained in the monomer (b1′) may be a straight chain alkyl group or a branched chain alkyl group.
Specific examples of the monomer (b1′) include the same as the above-mentioned monomer (a1′).
In addition, the monomer (b1′) may be used alone or in combination of two or more kinds.
However, as the monomer (b1′), butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferable, and butyl (meth)acrylate is more preferable.

The content of the structural unit (b1) is preferably 60 to 99.9% by mass, more preferably 70 to 99.7% by mass based on the total structural units (100% by mass) of the acrylic copolymer (B1). %, and more preferably 80 to 99.5 mass %.

Examples of the monomer (b2′) include the same hydroxyl group-containing monomers that can be selected as the above-mentioned monomer (a2′).
The monomer (b2′) may be used alone or in combination of two or more kinds.

The content of the structural unit (b2) is preferably 0.1 to 40% by mass, more preferably 0.3 to 30% by mass, based on all the structural units (100% by mass) of the acrylic copolymer (B1). %, and more preferably 0.5 to 20 mass %.

Further, the acrylic copolymer (B1) may further have a structural unit (b3) derived from a monomer (b3′) other than the monomers (b1′) and (b2′).
Examples of the monomer (b3′) include functional group-containing monomers other than the hydroxyl group-containing monomer that can be selected as the above-mentioned monomer (a2′), and the same as the above-mentioned monomer (a3′).

The content of the structural units (b1) and (b2) in the acrylic copolymer (B1) is preferably 70 based on the total structural units (100 mass%) of the acrylic copolymer (B1). To 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.

On the other hand, examples of the isocyanate compound as the raw material of the acrylic urethane resin (I) include the same polyvalent isocyanate compounds as the raw material of the urethane prepolymer (UX) described above.
However, as the isocyanate compound, from the viewpoint of stretchability when an external force is applied, an isocyanate compound having no aromatic ring is preferable, and an aliphatic polyisocyanate and an alicyclic polyisocyanate are more preferable.

In the acrylic urethane-based resin (I), the ratio of the structural unit derived from the acrylic polyol compound to the structural unit derived from the isocyanate compound [acrylic polyol compound/isocyanate compound] is preferably 10/90 by mass ratio. To 90/10, more preferably 20/80 to 80/20, further preferably 30/70 to 70/30, and even more preferably 40/60 to 60/40.

{{Acrylic urethane resin (II)}}
Examples of the linear urethane prepolymer (UY), which is a raw material of the acrylic urethane resin (II), include a reaction product of a diol and a diisocyanate compound.
The diol and diisocyanate compound may be used alone or in combination of two or more kinds.
The mass average molecular weight (Mw) of the linear urethane prepolymer (UY) is preferably 1,000 to 300,000, more preferably 3,000 to 200,000, further preferably 5,000 to 100,000, and further more preferably It is 10,000 to 80,000, and more preferably 20,000 to 60,000.

Examples of the diol constituting the linear urethane prepolymer (UY) include alkylene glycol, polyether type diol, polyester type diol, polyester amide type diol, polyester/polyether type diol, and polycarbonate type diol.
Among these diols, polycarbonate type diols are preferable.

Examples of the diisocyanate compound that constitutes the linear urethane prepolymer (UY) include aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, and the like. From the viewpoint of stretchability when an external force is applied, alicyclic diisocyanate is used. Diisocyanates are preferred.
Specific diisocyanate compounds include those corresponding to the diisocyanate compounds among the compounds exemplified as the polyvalent isocyanate as the raw material of the urethane prepolymer (UX) described above.

The linear urethane prepolymer (UY) may be obtained by subjecting a diol and a diisocyanate compound to a chain extension reaction using a chain extender.
As the chain extender, the same chain extenders as those exemplified as the chain extender which can be used at the time of synthesizing the urethane prepolymer (UX) described above can be mentioned.

In one aspect of the present invention, the linear urethane prepolymer (UY) has an ethylenically unsaturated group at both ends.
As a method for introducing an ethylenically unsaturated group into both ends of a linear urethane prepolymer (UY), a terminal NCO group of a urethane prepolymer formed by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth)acrylate And a method of reacting with.
Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxy. Butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. are mentioned.

The vinyl compound (VY), which is a raw material of the acrylic urethane resin (II), contains at least a (meth)acrylic acid ester.
The (meth)acrylic acid ester is the same as the one corresponding to the (meth)acrylic acid ester among the monomers (a1′) to (a3′) used as the raw material of the above-mentioned acrylic copolymer (A1). There are things.
However, the (meth)acrylic acid ester is preferably one or more selected from alkyl(meth)acrylate and hydroxyalkyl(meth)acrylate, and it is more preferable to use alkyl(meth)acrylate and hydroxyalkyl(meth)acrylate in combination. preferable.

When alkyl(meth)acrylate and hydroxyalkyl(meth)acrylate are used in combination, the mixing ratio of hydroxyalkyl(meth)acrylate to 100 parts by mass of alkyl(meth)acrylate is preferably 0.1 to 100 parts by mass, more preferably The amount is preferably 0.2 to 90 parts by mass, more preferably 0.5 to 30 parts by mass, even more preferably 1.0 to 20 parts by mass, still more preferably 1.5 to 10 parts by mass.

The number of carbon atoms of the alkyl group contained in the alkyl (meth)acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, still more preferably 1 to 3.
Examples of the alkyl (meth)acrylate include the same as those exemplified as the monomer (a1′) that is a raw material of the acrylic copolymer (A1).

The hydroxyalkyl (meth)acrylate is the same as the hydroxyalkyl (meth)acrylate used for introducing an ethylenically unsaturated group at both ends of the linear urethane prepolymer (UY). Is mentioned.

Examples of vinyl compounds other than (meth)acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate. , (Meth)acrylonitrile, N-vinylpyrrolidone, (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, meth(acrylamide) and other polar group-containing monomers; and the like.
These may be used alone or in combination of two or more.

In one embodiment of the present invention, the content of the (meth)acrylic acid ester in the vinyl compound (VY) used as a raw material for the acrylic urethane resin (II) is the total amount (100% by mass) of the vinyl compound (VY). On the other hand, it is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass.

In one embodiment of the present invention, the total content of alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate in the vinyl compound (VY) used as a raw material for the acrylic urethane resin (II) is the vinyl compound (VY). Is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.

The acrylic urethane resin (II) can be obtained by polymerizing a linear urethane prepolymer (UY) which is a raw material and a vinyl compound (VY).
As a specific polymerization method, a radical generator is blended with a raw material linear urethane prepolymer (UY) and a vinyl compound (VY) in an organic solvent, and both ends of the linear urethane prepolymer (UY) are mixed. It can be synthesized by a radical polymerization reaction of a vinyl compound (VY) having an ethylenically unsaturated group as a starting point.
Examples of the radical generator to be used include diazo compounds such as azobisisobutyronitrile, benzoyl peroxide and the like.
In this radical polymerization reaction, a chain transfer agent such as a thiol group-containing compound may be added to the solvent to adjust the degree of polymerization of acrylic.

In the acrylic urethane resin (II) used in one embodiment of the present invention, the content ratio of the structural unit derived from the linear urethane prepolymer (UY) and the structural unit derived from the vinyl compound (VY) [(UY) /(VY)] in terms of mass ratio, preferably 10/90 to 80/20, more preferably 20/80 to 70/30, further preferably 30/70 to 60/40, further more preferably 35/. 65-55/45.

{Olefin resin}
The olefin resin contained in the composition (y) as the non-adhesive resin (y1) is a polymer having at least a constitutional unit derived from an olefin monomer.
The olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, and specific examples thereof include ethylene, propylene, butylene, isobutylene and 1-hexene.
Among these, ethylene and propylene are preferable.

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 or other polyethylene resin; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); ethylene-vinyl acetate copolymer (EVA); ethylene-propylene-(5-ethylidene-2-norbornene), etc. Olefin-based terpolymer; and the like.

In one aspect of the present invention, the olefin-based resin may be a modified olefin-based resin that is further subjected to at least one modification selected from acid modification, hydroxyl group modification, and acrylic modification.

For example, as an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification, a modified polymer obtained by graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof to the aforementioned unmodified olefin resin. Is mentioned.
Examples of the unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth)acrylic acid, maleic anhydride, itaconic anhydride. , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride and the like.
The unsaturated carboxylic acid or its anhydride may be used alone or in combination of two or more kinds.

An acrylic-modified olefin resin obtained by subjecting an olefin resin to acrylic modification is a modified one obtained by graft-polymerizing an alkyl (meth)acrylate as a side chain on the above-mentioned unmodified olefin resin which is the main chain. Polymers may be mentioned.
The number of carbon atoms of the alkyl group contained in the alkyl (meth)acrylate is preferably 1 to 20, more preferably 1 to 16, and further preferably 1 to 12.
Examples of the alkyl (meth)acrylate include the same compounds that can be selected as the above-mentioned monomer (a1′).

Examples of the hydroxyl group-modified olefin resin obtained by subjecting the olefin resin to hydroxyl group modification include modified polymers obtained by graft-polymerizing a hydroxyl group-containing compound on the above-mentioned unmodified olefin resin which is the main chain.
Examples of the hydroxyl group-containing compound include the same hydroxyl group-containing monomer that can be selected as the above-mentioned monomer (a2′).

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, still more preferably 20,000 to 400,000, still more preferably 50,000 to 300,000. is there.

(Resin other than acrylic urethane resin and olefin resin)
In one aspect of the present invention, the composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester resin such as phthalate; Polystyrene; Acrylonitrile-butadiene-styrene copolymer; Cellulose triacetate; Polycarbonate; Polyurethane not applicable to acrylic urethane resin; Polymethylpentene; Polysulfone; Polyetheretherketone; Polyethersulfone; Polyphenylene Sulfides; polyimide resins such as polyetherimide and polyimide; polyamide resins; acrylic resins; fluorine resins and the like.

However, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y) and the printing/printing layer (Z), and further from the viewpoint of further improving the interfacial adhesion between the base material layer (Y) and the pressure-sensitive adhesive layer (X). Therefore, it is preferable that the content ratio of the resin other than the acrylic urethane resin and the olefin resin in the composition (y) is small.
As a specific content ratio of the resin other than the acrylic urethane resin and the olefin resin, the non-adhesive resin (y1) selected from the group consisting of the acrylic urethane resin and the olefin resin contained in the composition (y). Is preferably less than 30 parts by mass, more preferably less than 20 parts by mass, more preferably less than 10 parts by mass, still more preferably less than 5 parts by mass, still more preferably less than 1 part by mass, relative to the total amount of 100 parts by mass of .

(Crosslinking agent)
In one aspect of the present invention, when the composition (y) contains an acrylic urethane-based resin, the acrylic urethane-based resin is cross-linked, and therefore it is more preferable to further contain a crosslinking agent.
As the cross-linking agent, for example, an isocyanate compound as the cross-linking agent is preferable.
As the isocyanate compound as the crosslinking agent, various isocyanate compounds can be used as long as they react with the functional groups of the acrylic urethane resin to form a crosslinked structure.
As the isocyanate compound, a polyisocyanate compound having two or more isocyanate groups per molecule is preferable.

Examples of polyisocyanate compounds include diisocyanate compounds, triisocyanate compounds, tetraisocyanate compounds, pentaisocyanate compounds, hexaisocyanate compounds, and the like. More specifically, aromatic polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; dicyclohexylmethane-4,4-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene. Alicyclic isocyanate compounds such as diisocyanate and hydrogenated xylylene diisocyanate; aliphatic isocyanate compounds such as pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate.
Further, biuret bodies of these isocyanate compounds, isocyanurate bodies and adduct bodies which are reaction products of these isocyanate compounds with non-aromatic low molecular weight active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane and castor oil. Modified products can also be used.

Among these isocyanate compounds, an aliphatic isocyanate compound is preferable, an aliphatic diisocyanate compound is more preferable, and pentamethylene diisocyanate, hexamethylene diisocyanate and heptamethylene diisocyanate are further preferable.
In the composition (y), one type of isocyanate compound may be used alone, or two or more types may be used in combination.

In the composition (y), the content ratio of the acrylic urethane-based resin and the isocyanate-based compound as the cross-linking agent is 100% by mass in terms of solid content of the acrylic urethane-based resin in total, and the isocyanate-based compound as the cross-linking agent. The amount of the compound is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, still more preferably 3 to 15 parts by mass.

(catalyst)
In one aspect of the present invention, when the composition (y) contains an acrylic urethane resin and the cross-linking agent, the composition (y) further preferably contains a catalyst together with the cross-linking agent.
The catalyst is preferably a metal catalyst, more preferably a metal catalyst excluding a tin compound having a butyl group.
Examples of the metal-based catalyst include a tin-based catalyst, a bismuth-based catalyst, a titanium-based catalyst, a vanadium-based catalyst, a zirconium-based catalyst, an aluminum-based catalyst, and a nickel-based catalyst. Among these, a tin-based catalyst or a bismuth-based catalyst is preferable, and a tin-based catalyst or a bismuth-based catalyst excluding a tin-based compound having a butyl group is more preferable.

Examples of the tin-based catalyst include organometallic compounds of tin and compounds having a structure such as alkoxide, carboxylate, and chelate. Among them, acetylacetone complex, acetylacetonate, octylic acid compound or naphthene is preferable. Examples thereof include acid compounds.
Similarly, bismuth-based catalyst, titanium-based catalyst, vanadium-based catalyst, zirconium-based catalyst, aluminum-based catalyst, or nickel-based catalyst, respectively, is an organometallic compound of bismuth, titanium, vanadium, zirconium, aluminum, or nickel. Examples thereof include compounds having a structure such as alkoxide, carboxylate and chelate, and preferable examples thereof include acetylacetone complexes of these metals, acetylacetonates, octylic acid compounds and naphthenic acid compounds.

Specific examples of the metal acetylacetone complex include acetylacetone tin, acetylacetone titanium, acetylacetone vanadium, acetylacetone zirconium, acetylacetone aluminum, acetylacetone nickel and the like.
Specific examples of acetylacetonate include tin acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate, vanadium acetylacetonate, zirconium acetylacetonate, aluminum acetylacetonate, and nickel acetylacetonate.
Specific examples of the octylic acid compound include bismuth 2-ethylhexylate, nickel 2-ethylhexylate, zirconium 2-ethylhexylate, and tin 2-ethylhexylate.
Specific examples of the naphthenic acid compound include bismuth naphthenate, nickel naphthenate, zirconium naphthenate, tin naphthenate and the like.

As the tin-based catalyst, a general formula RxSn(L) _(4-X) (In the general formula, R is an alkyl group having 1 to 25 carbon atoms, preferably an alkyl group having 1 to 3 or 5 to 25 carbon atoms, or A tin compound represented by the formula (1) is an aryl group, L is an organic group other than an alkyl group and an aryl group, or an inorganic group, and x is 1, 2 or 4.

In the general formula RxSn(L) _(4-X) , the alkyl group of R is more preferably an alkyl group of 5 to 25 carbon atoms, further preferably an alkyl group of 5 to 20 carbon atoms, and the aryl group of R is The carbon number is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable. When two or more R's are present in one molecule, each R may be the same or different.
Further, L is preferably an aliphatic carboxylic acid having 2 to 20 carbon atoms, an aromatic carboxylic acid, or an aromatic sulfonic acid, and more preferably an aliphatic carboxylic acid having 2 to 20 carbon atoms. Examples of the aliphatic carboxylic acid having 2 to 20 carbon atoms include an aliphatic monocarboxylic acid having 2 to 20 carbon atoms and an aliphatic dicarboxylic acid having 2 to 20 carbon atoms. When two or more L's are present in one molecule, each L may be the same or different.

In the composition (y), the catalyst may be used alone or in combination of two or more.
In the composition (y), the content ratio of the acrylic urethane-based resin and the catalyst is preferably 0.001 to 5 parts by mass in terms of solid content of the catalyst based on 100 parts by mass of the total acrylic urethane-based resin. It is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 parts by mass.

(Base material additive)
In one aspect of the present invention, the composition (y) may contain an additive for a base material contained in a base material included in a general pressure-sensitive adhesive sheet, as long as the effect of the present invention is not impaired.
Examples of such a base material additive include an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, and a colorant.
In addition, these additives for base materials may be used alone or in combination of two or more kinds.
When these additives for base materials are contained, the content of each additive for base materials is preferably 0.0001 to 20 parts by mass, relative to 100 parts by mass of the non-adhesive resin (y1). It is more preferably 0.001 to 10 parts by mass.

(Diluting solvent)
In one aspect of the present invention, the composition (y) may be in the form of a solution containing water or an organic solvent as a diluting solvent together with the above-mentioned various active ingredients.
Examples of the organic solvent include the same organic solvents as those used when the composition (x) is prepared in the form of a solution.
The diluent solvent contained in the composition (y) may be used alone or in combination of two or more kinds.

When the composition (y) contains a diluting solvent and is in the form of a solution, the concentration of the active ingredient of the composition (y) is, independently, preferably 0.1 to 60% by mass, more preferably 0. The amount is 5 to 50% by mass, more preferably 1.0 to 40% by mass.

[Physical Properties of Base Material Layer (Y) Formed from Composition (y)]
The breaking elongation of the base material layer (Y) formed from the composition (y) is preferably 100% or more, more preferably 120% or more, further preferably 200% or more, still more preferably 350% or more. The upper limit of the breaking elongation is not particularly limited, but is preferably 1,000% or less.
The breaking strength of the base material layer (Y) formed from the composition (y) is preferably 30 MPa or more, more preferably 60 MPa or more.
The breaking elongation and breaking strength of the base material layer (Y) are the coating film (y′) composed of the composition (y) under the same coating amount and drying conditions as in the case of producing a pressure-sensitive adhesive sheet for printing and printing. ) Is the object of measurement. The specific measuring method is the same as the measuring method of breaking elongation and breaking strength of the pressure-sensitive adhesive sheet for printing and printing described in Examples.

<<Printing print layer (Z)>>
The print-printing layer (Z) is a layer formed by drying a coating film (z′) made of the composition (z) containing the non-adhesive resin (z1), and made of the above-mentioned composition (y). It is formed by drying simultaneously with the coating film (y').

[Composition (z)]
The composition (z), which is a material for forming the printing/printing layer (Z), contains a non-adhesive resin (z1). Further, the composition (z) may contain a resin other than the non-adhesive resin (z1) within a range that does not impair the effects of the present invention, and may also be used as a diluting solvent and/or a general printing/printing layer. It may contain included additives.

(Non-adhesive resin (z1))
The non-adhesive resin (z1) is a non-adhesive resin different from the above-mentioned non-adhesive resin (y1), preferably a polyester resin and/or a urethane-modified polyester resin, more preferably a urethane-modified resin. It is a polyester resin.
Moreover, when the non-adhesive resin (z1) is a copolymer having two or more kinds of constitutional units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and It may be any of graft copolymers.
In addition, in one aspect of the present invention, as long as the effect of the present invention is not impaired, as the non-adhesive resin (z1), a resin contained in a general print-printing layer other than the polyester resin and the urethane-modified polyester resin is used. May be included.

The content of the non-adhesive resin (z1) in the composition (z) is preferably 50 to 100% by mass, more preferably 65% by mass based on the total amount (100% by mass) of the active ingredients of the composition (z). To 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
The total content of the polyester resin and/or the urethane-modified polyester resin in the non-adhesive resin (z1) is the total amount of the non-adhesive resin (z1) contained in the composition (z) (100% by mass). ), preferably 30 to 100% by mass, more preferably 50 to 100% by mass, further preferably 70 to 100% by mass, still more preferably 85 to 100% by mass.

The polyester resin that can be used as the non-adhesive resin (z1) is a copolymer obtained by a polycondensation reaction of an acid component and a diol component or a polyol component, and includes a modified product of the copolymer. .
The polycondensation reaction is performed by a general polyesterification reaction such as a direct esterification method or a transesterification method.
These polyester resins may be used alone or in combination of two or more.

Examples of the acid component include dicarboxylic acids such as terephthalic acid, phthalic acid, sulfoterephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 5-sodiumsulfoisophthalic acid. Aromatic dicarboxylic acids such as acids, 5-potassium sulfoisophthalic acid or their anhydrides or esters; pimelic acid, suberic acid, azelaic acid, oxalic acid, sebacic acid, succinic acid, adipic acid, undecylenic acid, dodecanedicarboxylic acid Or aliphatic dicarboxylic acids such as anhydrides or esters thereof; 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid or alicyclic dicarboxylic acids such as anhydrides or esters thereof, and the like.

Examples of the diol component or the polyol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, etc. Aliphatic glycols; alicyclic glycols such as 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol; p-xylene glycol, bisphenol A, etc. Aromatic glycol; and the like.
Examples of the urethane polyester-based resin that can be used as the non-adhesive resin (z1) include those having a urethane bond in addition to the polyester-based resin. The urethane-modified polyester resin can be obtained, for example, by reacting a polyester resin having two or more functional groups such as hydroxyl groups in one molecule with a polyisocyanate compound.

As the polyisocyanate compound, the same polyisocyanate compound as the above-mentioned isocyanate compound as a crosslinking agent which may be contained in the composition (y) can be used. The polyisocyanate compound used for the urethane modification of the polyester resin may be used alone or in combination of two or more.
The urethane-modified polyester resin is preferably a urethane-modified polyester resin having a basic structure of aromatic polyester. The basic structure of the aromatic polyester is one having a repeating unit derived from an aromatic compound in the polyester structure of the main chain, and for example, one or both of dicarboxylic acid and glycol compound of a part or all of the copolymerization raw material. Is an aromatic compound.

As the non-adhesive resin (z1), one type of polyester resin or urethane modified polyester type resin may be used alone, or two or more types selected from the group consisting of polyester type resin and urethane modified polyester type resin are combined. You may use it.
The non-adhesive resin (z1) more preferably contains two kinds of resins having different glass transition points, and further preferably contains two kinds of urethane-modified polyester resins having different glass transition points.

When the composition (z) contains, as the non-adhesive resin (z1), two kinds of resins having different glass transition points, the difference between the glass transition points of the resins is preferably 20° C. or higher, more preferably 30° C. Or more, more preferably 50° C. or more, still more preferably 70° C. or more.
In this case, the glass transition point of the resin having a relatively high glass transition point is preferably 40 to 105°C, more preferably 50 to 100°C, and further preferably 70 to 95°C.
The glass transition point of the resin having a relatively low glass transition point is preferably -30 to 15°C, more preferably -25 to 5°C.
When the composition (z) contains two kinds of resins having different glass transition points as the non-adhesive resin (z1), the content of the resin having a relatively low glass transition point is relatively low. It is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and still more preferably 15 to 40 parts by mass with respect to 100 parts by mass in total of the high resin and the low resin.
The value and content of each glass transition point are the same when a polyester resin or a urethane-modified polyester resin is used as the resin having a different glass transition point.
The number average molecular weight (Mn) of the polyester resin and urethane-modified polyester resin used as the non-adhesive resin (z1) is preferably 5,000 to 100,000, and more preferably 10,000 to 60,000.

(Crosslinking agent)
The composition (z), which is a material for forming the print/printing layer (Z), further preferably contains an isocyanate compound as a crosslinking agent together with the polyester resin and/or the urethane-modified polyester resin.
As the isocyanate compound as a crosslinking agent, various isocyanate compounds can be used as long as they react with a functional group such as a hydroxyl group of the polyester resin and the urethane-modified polyester resin to form a crosslinked structure. ..
The isocyanate compound is the same as the isocyanate compound as the cross-linking agent which may be contained in the composition (y), and the preferred embodiments thereof are also the same.
In the composition (z), one type of isocyanate compound may be used alone, or two or more types thereof may be used in combination. In the composition (z), the polyester resin and/or the urethane-modified polyester resin is used. With respect to the total content of the polyester resin and/or the urethane-modified polyester resin in the solid content, the isocyanate compound as the crosslinking agent is preferably 1 To 30 parts by mass, more preferably 2 to 20 parts by mass, still more preferably 3 to 15 parts by mass.

(catalyst)
The composition (z), which is a material for forming the printing/printing layer (Z), further preferably contains a catalyst together with the isocyanate compound as the crosslinking agent.
Examples of the catalyst that may be contained in the composition (z) include the same catalysts that may be contained in the composition (y) described above, and the preferable embodiments thereof are also the same.

In the composition (z), the catalyst may be used alone or in combination of two or more.
In the composition (z), the content ratio of the polyester-based resin and/or urethane-modified polyester-based resin and the catalyst is such that the catalyst is solid with respect to 100 parts by mass in total of the polyester-based resin and/or the urethane-modified polyester-based resin. The amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and further preferably 0.1 to 2 parts by mass.
When a metal-based catalyst is used as the catalyst, the metal-based catalyst is preferably 0.001 to 5 parts by mass in terms of metal amount, based on 100 parts by mass of the polyester resin and/or the urethane-modified polyester-based resin. It is more preferably 0.005 to 2 parts by mass, and even more preferably 0.01 to 1 part by mass.

(Diluting solvent)
In one aspect of the present invention, the composition (z) may be in the form of a solution containing water or an organic solvent as a diluting solvent together with the above-mentioned various active ingredients.
Examples of the organic solvent include the same organic solvents as those used when the composition (x) is prepared in the form of a solution.
The diluent solvent contained in the composition (z) may be used alone or in combination of two or more kinds.

When the composition (z) contains a diluting solvent and is in the form of a solution, the active ingredient concentration of the composition (z) is independently 0.5 to 40% by mass, and more preferably 1. It is 0 to 30 mass %.

In one aspect of the present invention, the composition (z) may be mixed with various fillers such as organic fillers and inorganic fillers in order to improve the slipperiness and to obtain a matte feel.
Examples of the organic filler include polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, acrylic resin such as methyl methacrylate, and resin powder such as a mixture thereof.
Examples of the inorganic filler include inorganic oxides such as silica and alumina, and metal powders such as gold powder and silver powder.
When the composition (z) contains a filler, the compounding amount of the filler is preferably 100 parts by mass of the total amount of the non-adhesive resin (z1) and/or the crosslinking agent in the composition (Z). Is 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass.

<Physical properties of adhesive sheet for printing and printing>
The thickness of the laminate of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is preferably 2 to 90 μm, more preferably 5 to 80 μm, still more preferably 10 to 70 μm, still more preferably 15 to 55 μm. ..

The thickness of the pressure-sensitive adhesive layer (X) is preferably 0.5 to 50.0 μm, more preferably 1.0 to 40.0 μm, still more preferably 2.0 to 30.0 μm, still more preferably 3.0. ˜25.0 μm.

The thickness of the base material layer (Y) is preferably 0.3 to 50.0 μm, more preferably 0.5 to 40.0 μm, still more preferably 1.0 to 35.0 μm, and even more preferably 5.0. ˜30.0 μm, and even more preferably 8.0 to 24.0 μm.

The thickness of the print/printing layer (Z) is preferably 0.1 to 20.0 μm, more preferably 0.2 to 15.0 μm, still more preferably 0.3 to 10.0 μm, still more preferably 0.4. ~ 5.0 μm.

In the present specification, the thickness of the laminate is a value measured by using a constant pressure thickness measuring device in accordance with JIS K6783, Z1702, Z1709, and specifically measured by the method described in Examples. Means the value that has been set.
Further, the thickness of each layer constituting the laminated body may be measured by the same method as the thickness of the laminated body described above, and for example, a cross section obtained by cutting the laminated body in the thickness direction is observed with a scanning electron microscope. Then, the thickness ratio of each layer may be measured and calculated from the thickness of the laminate measured by the above method.

In the pressure-sensitive adhesive sheet for printing and printing of one aspect of the present invention, the thickness ratio of the pressure-sensitive adhesive layer (X) to the total thickness 100 of the base material layer (Y) and the printing and printing layer (Z) is preferably 20 to. 110, more preferably 20 to 100, still more preferably 23 to 98, even more preferably 25 to 95, still more preferably 28 to 90.

In the laminate having the pressure-sensitive adhesive sheet for printing and printing of the present invention, as described above, a mixed layer occurs between the two coating films during the drying process of the coating film, and thus the printing and printing layer (Z) and the base material layer (Y). In some cases, the interface with and the interface between the base material layer (Y) and the pressure-sensitive adhesive layer (X) may be unclear enough to disappear.
When a mixed layer is formed between two coating films and between the formed layers, for example, as described above, the cross section obtained by cutting the laminated body in the thickness direction is observed with a scanning electron microscope to determine the thickness of each layer. In the case of measuring the respective thickness ratios, and when a mixed layer is generated between the printed layer (Z) and the base material layer (Y), the mixed layer passes through the middle point in the thickness direction. Moreover, the thickness ratio of each layer may be measured on the assumption that an interface exists on a surface parallel to the surface of the printed layer (Z) opposite to the surface of the base material layer (Y).

The curved surface followability determined by the method described in the below-mentioned examples, which the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention has, is preferably 5. It is 0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less, even more preferably 2.5 mm or less, even more preferably 2.0 mm or less, even more preferably 1.5 mm or less.
The suitable range is the same regardless of whether the adherend is made of polypropylene or polyethylene in the evaluation method described in Examples described later.

The pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention on the surface of the adhesive is preferably 3.0 N/25 mm or more, more preferably 4.0 N/25 mm or more, and further preferably 5 It is 0.0 N/25 mm or more, more preferably 10.0 N/25 mm or more.
In addition, the value of the said adhesive force means the value measured by the method as described in an Example.

The breaking strength of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is preferably 5 MPa or more, more preferably 8 MPa or more, still more preferably 10 MPa or more, and preferably 50 MPa or less, more preferably 40 MPa or less, further preferably. Is 32 MPa or less.
The elongation at break of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is preferably 100% or more, more preferably 150% or more, still more preferably 200% or more, still more preferably 250% or more. The upper limit of the breaking elongation is not particularly limited, but is preferably 1,000% or less.

The yield strength of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is preferably 0.5 MPa or more, more preferably 1.0 MPa or more, still more preferably 1.5 MPa or more, and preferably 500 MPa or less, more preferably Is 250 MPa or less, more preferably 100 MPa or less, even more preferably 50 MPa or less, even more preferably 25 MPa or less.
The yield elongation of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is preferably 3.0% or more, more preferably 4.0% or more, still more preferably 4.5% or more, still more preferably 4% or more. It is 8% or more. The upper limit of the yield elongation is not particularly limited, but is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less, still more preferably 8% or less.

The elastic modulus (tensile elastic modulus) of the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is preferably 1.0 MPa or more, more preferably 5.0 MPa or more, further preferably 10 MPa or more, even more preferably 25 MPa or more. , And preferably 500 MPa or less, more preferably 450 MPa or less, still more preferably 400 MPa or less.
The values of the breaking strength, the breaking elongation, the yield strength, the yield elongation, and the elastic modulus described above mean the values measured by the method described in Examples.

<Release material>
The pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention comprises a surface of the pressure-sensitive adhesive layer (X) opposite to the base material layer (Y) and/or a base material layer (Y) of the print/printing layer (Z). May further have a release material on the opposite surface.
When a release material is used for both the pressure-sensitive adhesive layer (X) and the print layer (Z) on the surface, each release material may be adjusted so that the difference in the release force is different. Good.
As the release material, a release sheet that has been subjected to a double-sided release treatment, a release sheet that has been subjected to a single-sided release treatment, and the like are used, and examples include a release agent coated on a base material for a release material.

Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, and polyethylene resin. Plastic films such as olefin resin films; and the like.

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

The thickness of the release material is not particularly limited, but is preferably 10 to 200 μm, more preferably 25 to 170 μm, further preferably 30 to 125 μm, and further preferably 35 to 80 μm.

[Method for producing adhesive sheet for printing and printing]
The method for producing the pressure-sensitive adhesive sheet for printing and printing of the present invention is preferably a method having the following steps (1A) and (2A).
Further, the method for producing a pressure-sensitive adhesive sheet for printing/printing of the present invention can improve the productivity because the number of steps in producing the pressure-sensitive adhesive sheet for printing/printing can be reduced as compared with the conventional production method. it can.
Step (1A): a step of directly laminating a coating film (z') made of the composition (z) and a coating film (y') made of the composition (y) in this order.
Step (2A): a step of drying the coating film (z') and the coating film (y') at the same time to form the printed print layer (Z) and the base material layer (Y).
Hereinafter, steps (1A) and (2A) will be described.

<Step (1A)>
In the step (1A), the coating film (z′) and the coating film (y′) may be formed by, for example, forming the coating film (z′) and then forming the coating film (y′) on the coating film (z′). It may be a sequential formation method such as forming the coating composition'), but from the viewpoint of productivity, the composition (z) and the composition (y) are simultaneously coated to form the coating film (z') and the coating film (y'). A method of simultaneously forming is preferable.
From the viewpoint of handleability, the coating film (z') or coating film (y') is preferably formed on the release-treated surface of the release material.
When a coating film (z') is formed on a release agent and at least the coating film (y') contains a diluting solvent, the coating film (z') is treated on the release treatment surface of the release material from the viewpoint of productivity. It is more preferable to form the coating film (y′) on the coating film (z′) on the above.
That is, when each coating film is dried, the gas derived from the diluting solvent generated from the coating film (y′) is not permeated through the coating film (z′) and is released into the air so that each coating film is released. Is more preferably formed. By doing so, it is possible to prevent the vaporization or volatilization of the diluent solvent from being hindered by the coating film (z′) and the print printing layer (Z) having relatively low gas permeability. As a result, it is possible to prevent poor drying of each coating film and further improve productivity.

As the coater used for coating the composition (z) and the composition (y) when sequentially forming the coating film (z′) and the coating film (y′), for example, a spin coater, a spray coater, a bar coater, A knife coater, a roll coater, a knife roll coater, a blade coater, a gravure coater, a curtain coater, a die coater and the like can be mentioned.

Examples of the coater used when the composition (z) and the composition (y) are simultaneously applied include a multilayer coater, and specifically, a multilayer curtain coater, a multilayer die coater and the like. Among these, the multilayer die coater is preferable from the viewpoint of operability.

From the viewpoint of facilitating the formation of each coating film and improving the productivity, it is preferable that the composition (z) and the composition (y) each independently further contain a diluting solvent.
As the diluting solvent, the above diluting solvent described in the section of the pressure-sensitive adhesive sheet for printing and printing can be used.
The concentration of the active ingredient in the solution obtained by blending each composition with a diluting solvent is as described above in the section of the pressure-sensitive adhesive sheet for printing and printing.

The coating amount of the coating film (z′) is preferably 0.1 to 50.0 g/m ² , more preferably 0.5 to 30.0 g/m ² , and still more preferably 1.0 to 20.0 g/m ² . ² , and more preferably 3.0 to 10.0 g/m ² .

The coating amount of the coating film (y′) is preferably 1.0 to 150 g/m ² , more preferably 5.0 to 120 g/m ² , further preferably 10.0 to 100 g/m ² , and even more preferably It is 20.0 to 95.0 g/m ² , and more preferably 40.0 to 95.0 g/m ² .

The ratio of the coating amount (g/m ² ) of the coating film (z′) to the total coating amount (g/m ² ) of the coating film (z′) and the coating film (y′) is preferably 1 to 80, more preferably 2 to 50, still more preferably 3 to 30, still more preferably 4 to 20, still more preferably 5 to 15.

In addition, in this step (1A), after forming one or more coating films of the coating film (z') and the coating film (y'), before the step (2A) described later, the curing reaction of the coating film is You may perform a pre-drying process which does not progress.
For example, a pre-drying treatment may be carried out each time each coating film (z′) and coating film (y′) is formed. After forming the coating film of the layers, the two layers may be simultaneously subjected to a pre-drying treatment. When performing pre-drying, from the viewpoint of improving the interfacial adhesion between the printed layer (Z) and the base material layer (Y), two layers of the coating film (z′) and the coating film (y′) are It is preferable that the two layers are pre-dried at the same time after forming the coating film.
In the present step (1A), the drying temperature at the time of performing the pre-drying treatment is usually set appropriately within a temperature range where curing of the formed coating film does not proceed, but preferably in the step (2A). Below the drying temperature.
The specific drying temperature indicated by the definition "less than the drying temperature in the step (2A)" is preferably 10 to 45°C, more preferably 10 to 34°C, and further preferably 15 to 30°C.

<Step (2A)>
In the step (2A), the coating film (z') and the coating film (y') are simultaneously dried to form the laminate.
In this drying process, a mixed layer is formed at the interface between the coating film (z′) and the coating film (y′), and the non-adhesive resin (z1) and the non-adhesive resin (y1) are entangled and dried. It is considered that the curing improves the interfacial adhesion between the printed print layer (Z) and the base material layer (Y).

The drying temperature of the coating film in the step (2A) is preferably 60 to 150°C, more preferably 70 to 145°C, further preferably 80 to 140°C, still more preferably 90 to 135°C.

The method including the steps (1A) and (2A) further includes a step of forming the pressure-sensitive adhesive layer (X).
Here, as a method of forming the pressure-sensitive adhesive layer (X), for example, printing of the base material layer (Y) obtained in the step (2A) by heating and melting the composition (x) containing the pressure-sensitive adhesive resin It may be extrusion-laminated on the surface opposite to the printing layer, and a coating film (x′) composed of the composition (x) containing an adhesive resin may be formed on the surface of the base material layer (Y). It may be formed and dried.
In addition, for example, the pressure-sensitive adhesive layer (X) is a product obtained by previously extruding or drying the coating film (x′) and then pasting it onto the base material layer (Y) directly or through another layer. May be

When the method of forming the coating film (x′) is used, for example, the method of the following step (3A) or (3A′) can be mentioned.
Step (3A): The composition (x) containing an adhesive resin is applied to the surface of the base material layer (Y) obtained in step (2A) on the side opposite to the printing and printing layer (Z). A step of forming a coating film (x′) and drying the coating film to form a pressure-sensitive adhesive layer (Y).
Step (3A′): The composition (x) containing the adhesive resin is applied to the release-treated surface of the release material to form a coating film (x′), and the coating film is dried to form an adhesive layer. A pressure-sensitive adhesive formed on the release material on the surface of the base material layer (Y) obtained in the step (2A) on the opposite side to the print-printing layer (Z). Step of attaching layer (X).
The method for forming the coating film (x′) includes, for example, a spin coater, a spray coater, a bar coater, a knife coater, a roll coater, a knife roll coater, a blade coater, a gravure coater, a curtain coater, a die coater, and the like. ..
Further, from the viewpoint of facilitating the formation of the coating film (x′) and improving the productivity, it is preferable that the composition (x) further contains the above-mentioned diluent solvent. The concentration of the active ingredient in the solution obtained by blending the composition (x) with the diluting solvent is also as described above.

The coating amount of the coating film (x′) is preferably 0.1 to 100.0 g/m ² , more preferably 0.5 to 80.0 g/m ² , and still more preferably 1.0 to 70.0 g/m ² . ² , and more preferably 5.0 to 60.0 g/m ² .

The ratio of the coating amount (g/m ² ) of the coating film (x′) to the total coating amount (g/m ² ) 100 of the coating film (z′) and the coating film (y′) is preferably 1 to 100, more preferably 5 to 80, still more preferably 10 to 60, still more preferably 15 to 55.

The drying temperature of the coating film in the step (3A) or (3A′) is preferably 60 to 150° C., more preferably 70 to 145° C., further preferably 80 to 140° C., still more preferably 90 to 135° C. is there.

In addition, before providing the pressure-sensitive adhesive layer (X) in the step such as the step (3A) or (3A′), an intermediate layer (M) is further provided on the base material layer (Y), and the intermediate layer (M) is provided. The pressure-sensitive adhesive layer (X) may be provided on the surface of M) opposite to the substrate layer (Y) by the same method as described above.
Examples of the intermediate layer (M) include a primer layer for improving interfacial adhesion with the base material layer (Y) and the pressure-sensitive adhesive layer (X). The primer layer is not particularly limited, but has compatibility with both the non-adhesive resin (y1) forming the base material layer (Y) and the adhesive resin forming the adhesive layer (X). A primer layer formed of a resin can be used.

The method of forming the pressure-sensitive adhesive layer (X) is preferably a method of forming a coating film (x′) composed of the composition (x) by drying, more preferably a coating film (z′). And the coating film (y′) and the coating film (x′) are dried at the same time.
Therefore, the method for producing a pressure-sensitive adhesive sheet for printing and printing is more preferably a method having the following steps (1B) and (2B).
Step (1B): a coating film (z') composed of the composition (z), a coating film (y') composed of the composition (y), and a coating film (x') composed of the composition (x). The process of directly laminating and forming in this order.
Step (2B): a step of drying the coating film (z'), the coating film (y'), and the coating film (x') at the same time to form the laminate.
The steps (1B) and (2B) will be described below.

<Step (1B)>
In the step (1B), the coating film (z′), the coating film (y′), and the coating film (x′) may be formed by, for example, forming the coating film (z′) and then forming the coating film (z′). A coating film (y') is formed on the coating composition ('), and then a coating film (x') is further formed on the coating film (y'). However, from the viewpoint of productivity, the composition ( Preferred is a method of simultaneously applying z), the composition (y), and the composition (z) to simultaneously form the coating film (z′), the coating film (y′) and the coating film (x′).
From the viewpoint of handleability and productivity, it is preferable to form the coating film (z') on the release-treated surface of the release material.
When a coating film (z′) is formed on a release agent and at least the coating film (y′) or the coating film (x′) contains a diluting solvent, from the viewpoint of productivity, the release material, the coating film ( It is more preferable to form z′), the coating film (y′), and the coating film (x′) in this order.
That is, when each coating film is dried, the gas derived from the diluting solvent generated from the coating film (y′) and/or the coating film (x′) does not permeate through the coating film (z′) and is in the air. More preferably, each coating is formed so as to be released into As described above in the explanation of the step (1A), it is possible to prevent the evaporation or volatilization of the diluent solvent from being hindered by the coating film (z′) and the print printing layer (Z) having relatively low gas permeability. As a result, it is possible to prevent poor drying of each coating film and further improve productivity.

Examples of the coater used when sequentially forming each coating film include the above-mentioned coaters and the like.
The coater used when the composition (z), the composition (y), and the composition (x) are applied simultaneously includes a multi-layer coater capable of simultaneously applying at least three layers. Specific examples include a multilayer curtain coater and a multilayer die coater. Among these, a multi-layer die coater capable of simultaneously coating three or more layers is preferable from the viewpoint of operability.

From the viewpoint of facilitating the formation of each coating film and improving the productivity, the composition (x), the composition (y), and the composition (z) each independently contain a diluent solvent. Is preferred.
As the diluting solvent, the above diluting solvent described in the section of the pressure-sensitive adhesive sheet for printing and printing can be used.
The concentration of the active ingredient in the solution obtained by blending each composition with a diluting solvent is as described above in the section of the pressure-sensitive adhesive sheet for printing and printing.
Further, the suitable coating amounts of the coating film (z'), the coating film (y'), and the coating film (x') are as described above.

Of the coating amount (g/m ² ) of the coating film (z′), the coating film (y′), and the coating film (x′) with respect to 100 (g/m ² ). The ratio is preferably 10 to 95, more preferably 20 to 90, further preferably 30 to 80, still more preferably 50 to 75.

Coating (z '), the coating (y'), and film (x ') the total coating amount of relative ^(g / m 2) 100, the coating film (z' coating amount of) of (g / ^{m 2)} The ratio is preferably 0.5 to 30, more preferably 1.0 to 20, still more preferably 4.0 to 15, still more preferably 5.0 to 10.

Coating (z '), the coating (y'), and film (x ') the total coating amount of relative ^(g / m 2) 100, the coating film (x' coating amount of) of (g / ^{m 2)} The ratio is preferably 1 to 100, more preferably 5 to 80, still more preferably 10 to 50, still more preferably 15 to 40.

In addition, in this step (1B), after forming one or more coating films of the coating film (z′), the coating film (y′), and the coating film (x′) and before the step (2B), Pre-drying treatment may be performed to such an extent that the curing reaction of the coating film does not proceed.
For example, a pre-drying treatment may be carried out each time the coating film (z′), the coating film (y′), and the coating film (x′) are formed. After forming the two-layer coating film (y'), the two layers may be pre-dried at the same time. The coating film (z'), coating film (y') and coating film (x') After forming the three-layer coating film, the three layers may be pre-dried at the same time. When performing pre-drying, from the viewpoint of improving the interfacial adhesion between the printed layer (Z) and the base material layer (Y), two layers of the coating film (z′) and the coating film (y′) are It is preferable that the two layers are pre-dried at the same time after forming the coating film. Further, from the viewpoint of improving the interfacial adhesion between the printed layer (Z) and the base material layer (Y) and the interfacial adhesion between the pressure-sensitive adhesive layer (X) and the base material layer (Y), a coating film It is more preferable that after forming the three-layer coating film of (z′), the coating film (y′) and the coating film (x′), the three layers are pre-dried at the same time.
In the present step (1B), the drying temperature at the time of performing the pre-drying treatment is usually set appropriately within a temperature range where curing of the formed coating film does not proceed, but preferably in the step (2B). It is below the drying temperature.
The specific drying temperature indicated by the definition "less than the drying temperature in step (2B)" is preferably 10 to 45°C, more preferably 10 to 34°C, and further preferably 15 to 30°C.

<Step (2B)>
In the step (2B), the coating film (z'), the coating film (y'), and the coating film (x') are simultaneously dried to form the laminate.
In this drying process, a mixed layer occurs at the interface between the coating film (z') and the coating film (y') and at the interface between the coating film (y') and the coating film (x'), and each coating film is The printing and printing layer (Z) and the base material layer (Y), and the base material layer (Y) and the pressure-sensitive adhesive layer, are obtained by drying and curing the adhesive resin and/or the non-adhesive resin contained therein in an intertwined state. It is considered that the interface adhesion with (X) is improved.

The drying temperature of the coating film in the step (2B) is preferably 60 to 150°C, more preferably 70 to 145°C, further preferably 80 to 140°C, still more preferably 90 to 135°C.

When the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is configured to further include a second pressure-sensitive adhesive layer (X2) other than the pressure-sensitive adhesive layer (X) on the surface of the pressure-sensitive adhesive layer (X), The second pressure-sensitive adhesive layer (X2) other than the agent layer (X) may be separately formed and attached to the formed laminate, or may be formed simultaneously with the formation of the laminate. For example, the second pressure-sensitive adhesive layer (X2) is formed from a composition which is a material for forming the second pressure-sensitive adhesive layer (X2) on the sticking surface of the pressure-sensitive adhesive layer (X) of the layered product after forming the layered product. May be formed by drying, and the second pressure-sensitive adhesive layer (X2) formed on the release-treated surface of a release material prepared separately is attached to the attachment surface of the pressure-sensitive adhesive layer (X). It may be formed.

The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples. The physical property values in the following production examples and examples are values measured by the following methods.

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

<Measurement of glass transition point>
According to JIS K 7121, the temperature was measured at a temperature rising rate of 20° C./min using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., product name “DSC Q2000”).

<Thickness of laminated body>
The thickness was measured using a constant pressure thickness meter manufactured by Teclock Co., Ltd. (model number: “PG-02J”, standard: JIS K6783, Z1702, Z1709 compliant).
Specifically, the total thickness of the print-printing pressure-sensitive adhesive sheet to be measured was measured, and the value obtained by subtracting the previously measured thickness of the release material was defined as the "thickness of the laminate".

<Thickness of each layer>
The release agent on the pressure-sensitive adhesive layer (X) and the print-printing layer (Z) of the pressure-sensitive adhesive sheet for printing and printing prepared in Examples and Comparative Examples was removed, and polyethylene was applied to the surface of the exposed pressure-sensitive adhesive layer (X). A terephthalate (PET) film (manufactured by Mitsubishi Plastics Co., Ltd., trade name “Diafoyle T-100”, thickness 50 μm) was attached to obtain a measurement sample.
The cross section in the thickness direction of the measurement sample cut in the direction perpendicular to the surface of the printed print layer (Z) was observed using a scanning electron microscope (manufactured by Hitachi, Ltd., product name "S-4700"). Of the pressure-sensitive adhesive layer (X), the base material layer (Y), and the print-printing layer (Z), the total thickness of the pressure-sensitive adhesive layer (X), the base material layer (Y), and the print-printing layer (Z). The ratio of each thickness (thickness ratio) was measured.
Then, based on the thickness ratio of each layer, the thickness of each layer was calculated from the actually measured value of the “thickness of the laminated body” measured by the method described above.

Production example 1
(Preparation of composition (x))
Acrylic copolymer (n-butyl acrylate (BA)/methyl methacrylate (MMA)/vinyl acetate (VAc)/2-hydroxyethyl acrylate (2HEA)=80.0/10.0/9, which is an adhesive resin. Acrylic copolymer having a constitutional unit derived from a raw material monomer consisting of 0.0/1.0 (mass ratio), mass average molecular weight (Mw): 1,000,000, diluent solvent: ethyl acetate, solid content concentration: 15 mass% ) 100 parts by mass (solid content ratio), as a tackifier, a rosin resin (manufactured by Arakawa Chemical Industry Co., Ltd., product name “KE-359”, softening point: 94 to 104° C.) 25 parts by mass (solid content ratio). ), and 1.62 parts by mass (solid content ratio) of an isocyanate cross-linking agent (manufactured by Mitsui Chemicals, Inc., product name “Takenate D-110N”) as a cross-linking agent, mixed and stirred uniformly. A composition (x) having a solid content concentration (active ingredient concentration) of 40 mass% was prepared.

Production example 2
(Preparation of composition (ya))
A solution of an acid-modified olefin resin that is a non-adhesive resin (y1) (manufactured by Mitsui Chemicals, Inc., product name "UNISTOL H-200", mass average molecular weight (Mw): 145,000, glass transition point: -53[deg.] C., diluting solvent: mixed solvent of methylcyclohexane and methyl ethyl ketone, solid content concentration (active ingredient concentration: 20% by mass) were used as the composition (ya).

Production Example 3
(Preparation of composition (yb))
(1) Synthesis of linear urethane prepolymer (UY) Isophorone diisocyanate was added to 100 parts by mass (solid content ratio) of a polycarbonate diol having a mass average molecular weight (Mw) of 1,000 in a reaction vessel under a nitrogen atmosphere. Blend so that the equivalent ratio of the hydroxyl groups of the polycarbonate diol and the isocyanate groups of isophorone diisocyanate will be 1/1, then add 160 parts by mass of toluene and stir the mixture under a nitrogen atmosphere while the concentration of the isocyanate groups is theoretical. 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 (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene was added, and the mixture was further heated at 80° C. until the isocyanate groups at both ends disappeared. The reaction was carried out for 6 hours to obtain a linear urethane prepolymer (UY) having a mass average molecular weight (Mw) of 29,000.
(2) Synthesis of Acrylic Urethane Resin (II) 100 parts by mass (solid content ratio) of the linear urethane prepolymer (UY) obtained in (1) above and methyl methacrylate (MMA) in a reaction vessel under a nitrogen atmosphere. 117 parts by mass (solid content ratio), 2-hydroxyethyl methacrylate (2-HEMA) 5.1 parts by mass (solid content ratio), 1-thioglycerol 1.1 parts by mass (solid content ratio), and toluene 50 parts by mass. Was added, and the temperature was raised to 105° C. with stirring.
In the meantime, a solution obtained by further diluting 2.2 parts by mass (solid content ratio) of a radical initiator (manufactured by Nippon Finechem Co., Ltd., product name “ABN-E”) with 210 parts by mass of toluene in the reaction vessel is 105 The solution was added dropwise over 4 hours while maintaining the temperature at ℃.
After the dropping of 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 composition (y-b) A cross-linking agent was added to 100 parts by mass (solid content ratio) of the solution of the acrylic urethane resin (II) obtained in (2) above, which is the non-adhesive resin (y1). Hexamethylene diisocyanate-based cross-linking agent (manufactured by Tosoh Corporation, product name "Coronate HL") 6.3 parts by mass (solid content ratio), and dioctyltin bis(2-ethylhexanoate) 1.4 as a catalyst. Parts by mass (solid content ratio) were blended and mixed. Further, the mixture was diluted with toluene and stirred uniformly to prepare a composition (yb) having a solid content concentration (active ingredient concentration) of 30% by mass.

Production Example 4
(Adjustment of composition (z))
As a non-adhesive resin (z1), 70 parts by mass of a urethane-modified polyester resin having a basic structure of an aromatic polyester (manufactured by Toyobo Co., Ltd., product name “Vylon UR1700”, number average molecular weight 16,000, glass transition point 92° C.) , And a urethane-modified polyester resin having a basic structure of an aromatic polyester (manufactured by Toyobo Co., Ltd., product name “Vylon UR8700”, number average molecular weight 32,000, glass transition point −22° C.) 30 parts by mass (non-adhesive resin (Z1) 100 parts by mass), a hexamethylene diisocyanate-based crosslinking agent (manufactured by Tosoh Corporation, product name "Coronate HL") 3 parts by mass as a crosslinking agent, and a bismuth-based catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. The name "Pucat 25", 25% by mass in terms of bismuth) 0.30 parts by mass, and a mixed solvent composed of toluene, methyl ethyl ketone, and cyclohexanone as a solvent (mass ratio: toluene:methyl ethyl ketone:cyclohexanone=10:10:1). After mixing and stirring uniformly, a composition (z) having a solid content concentration (active ingredient concentration) of 25 mass% was prepared.

Details of the release film and the base film used in the following Examples and Comparative Examples are shown below.
-Release film (1): manufactured by Lintec Co., Ltd., product name "SP-PET381031", polyethylene terephthalate (PET) film provided with a release agent layer formed of a silicone-based release agent on one surface, thickness: 38 µm.
-Release film (2): manufactured by Lintec Co., Ltd., product name "SP-PET382150", one side of a PET film provided with a release agent layer formed of a silicone-based release agent, thickness: 38 µm.
-Substrate film: manufactured by Toray Industries, Inc., product name "Lumirror 25T61M", biaxially oriented polyester (PET) film, thickness: 25 μm.

Example 1
(1) Formation of coating film A coating film (z') composed of the composition (z) prepared in Production Example 4 is formed on the release agent layer of the release film (1) which is a release material using an applicator. Then, a coating film (y') made of the composition (ya) prepared in Production Example 2 on the coating film (z), and a composition (Y') prepared in Production Example 1 on the coating film (y') ( A coating film (x') consisting of x) was successively formed.
The coating speed and the coating amount of each composition for forming the coating film (z'), the coating film (y') and the coating film (x') are the thickness of the laminate and each layer shown in Table 1. The thickness was adjusted to be
(2) Drying treatment The formed coating film (z'), coating film (y') and coating film (x') are simultaneously dried at a drying temperature of 110°C for 120 seconds to obtain a release agent layer of the release film (1). From the above, a layered product in which the layer (Z), the layer (Y) and the layer (X) were directly laminated was formed.
Then, the release agent layer of the release film (2) prepared separately from the release film on the layer (Z) was laminated on the surface of the exposed layer (X) to obtain a pressure-sensitive adhesive sheet for printing and printing.

Example 2
(1) Formation of coating film On the release agent layer of the release film (1) which is a release material, the composition (z) prepared in Production Example 4, the composition (yb) prepared in Production Example 3, and The composition (x) prepared in Production Example 1 was simultaneously coated in this order using a multi-layer die coater (width: 250 mm) at a coating speed of 30 m/min to obtain a coating film (z′) and a coating film (y ') and coating (x') were formed simultaneously in this order.
The coating amount of the composition for forming the coating film (z'), the coating film (y') and the coating film (x') is as shown in Table 1.
(2) Drying Treatment The formed coating film (z′), coating film (y′) and coating film (x′) are simultaneously dried at a drying temperature of 125° C. for 60 seconds to obtain a release agent layer of the release film (1). From the above, a layered product in which the layer (Z), the layer (Y) and the layer (X) were directly laminated was formed.
Then, the release agent layer of the release film (2) prepared separately from the release film on the layer (Z) was laminated on the surface of the exposed layer (X) to obtain a pressure-sensitive adhesive sheet for printing and printing.

Example 3
Examples except that the coating amount of each composition for forming the coating film (z'), the coating film (y') and the coating film (x') was changed to the amounts described in Table 1, respectively. A pressure-sensitive adhesive sheet for printing and printing was obtained in the same manner as in 2.

Examples 4 and 5
Instead of the composition (ya), the composition (yb) prepared in Production Example 3 was used, and the coating film (z'), the coating film (y') and the coating film (x'). ) The same method as in Example 1 except that the coating speed and the coating amount of each composition for forming the composition are the same as the thickness of the laminate and the thickness of each layer shown in Table 1, respectively. Using, a pressure-sensitive adhesive sheet for printing and printing was obtained.

Example 6
(1) Formation of coating film (z′) and coating film (y′) A composition (z prepared in Production Example 4) was prepared using an applicator on the release agent layer of the release film (1) which is a release material. A coating film (z′) composed of the above) was formed, and a coating film (y′) composed of the composition (yb) prepared in Production Example 3 was successively formed on the coating film (z).
The coating speed and coating amount of each composition for forming the coating film (z′) and the coating film (y′) are adjusted so as to be the thickness of the laminate and the thickness of each layer shown in Table 1. did.
(2) Drying treatment of (z') and coating film (y') The formed coating film (z') and coating film (y') are simultaneously dried at a drying temperature of 110°C for 120 seconds to obtain a release film (1 ), a layered product in which the layer (Z) and the layer (Y) were directly laminated was formed in this order.
(3) Formation of coating film (x′) In Production Example 1 using an applicator on the release agent layer of the release film (2) which is a release material prepared separately from the release film on the layer (Z). A coating film (x′) composed of the prepared composition (x) was formed.
The coating speed and coating amount of the composition (x) for forming the coating film (x′) were adjusted so as to be the thickness of the laminate and the thickness of each layer shown in Table 1.
(4) Drying Treatment of Coating Film (x′) The formed coating film (x′) was simultaneously dried at a drying temperature of 110° C. for 120 seconds to form a layer (X) on the release film.
(5) Formation of laminated body The surface of the exposed layer (X) was attached to the surface of the exposed layer (Y) to form a laminated body, and a pressure-sensitive adhesive sheet for printing and printing was obtained.

Comparative Example 1
A coating film (z') composed of the composition (z) prepared in Production Example 4 was formed on the release agent layer of the release film (1) which is a release material, and dried at a drying temperature of 110°C for 120 seconds to form a layer. (Z) was formed.
Further, a coating film (x′) composed of the composition (x) prepared in Production Example 1 is formed on the release agent layer of the release film (2) prepared separately from the release film on the layer (Z), It was dried at a drying temperature of 110° C. for 120 seconds to form a layer (X).
Then, a substrate film is laminated as a layer (Y) on the surface of the exposed layer (X), and the layer (Z) is further pressure-bonded on the substrate film at 140° C. with a heating roll. A laminated body was formed by laminating the laminated body, and an adhesive sheet for printing and printing in which the laminated body was sandwiched by two release materials was obtained.

Comparative example 2
A coating film (z') composed of the composition (z) prepared in Production Example 4 was formed on the release agent layer of the release film (1) which is a release material, and dried at a drying temperature of 110°C for 120 seconds to form a layer. (Z) was formed.
Further, a coating film (x′) composed of the composition (x) prepared in Production Example 1 is formed on the release agent layer of the release film (2) prepared separately from the release film on the layer (Z), It was dried at a drying temperature of 110° C. for 120 seconds to form a layer (X).
Further, a coating film (y′) was formed on the release agent layer of the separately prepared release film (1) using (ya) prepared in Production Example 2 and dried at a drying temperature of 110° C. for 120 seconds. And a layer (Y) was formed.
Then, the layer (Y) is laminated on the surface of the exposed layer (X), the release film (1) on the layer (Y) is removed, and the layer (Y) is exposed on the surface of the layer (Y). The layer (Z) was laminated at 140° C. while being pressure-bonded with a heating roll to form a laminate, and the double-sided pressure-sensitive adhesive sheet in which the laminate was sandwiched by two release materials was obtained.

Comparative Example 3
Instead of the composition (ya), the composition (yb) prepared in Production Example 3 was used, and the coating film (z'), the coating film (y') and the coating film (x'). The same method as in Comparative Example 2 except that the coating speed and the coating amount of each composition for forming a) are adjusted to be the thickness of the laminate and the thickness of each layer shown in Table 1, respectively. Using, a pressure-sensitive adhesive sheet for printing and printing was obtained.

The thickness of the laminate of the pressure-sensitive adhesive sheet for printing and printing prepared in Examples and Comparative Examples, and the thicknesses of the layer (X), the layer (Y), and the layer (Z) constituting the laminate are described above. It measured according to the method of. Moreover, the thickness ratio of the layer (X) to the total thickness 100 of the layer (Y) and the layer (Z) was calculated using the obtained results. The measurement results are shown in Table 1.

With respect to the pressure-sensitive adhesive sheets for printing and printing produced in Examples and Comparative Examples, various physical properties and properties were measured and evaluated using the methods described below. The obtained results are shown in Table 2.

<Break strength, elongation at break, yield strength, yield elongation, elastic modulus>
The pressure-sensitive adhesive sheet for printing and printing prepared in Examples and Comparative Examples was cut into a size of 120 mm in length×15 mm in width, and each release material on the pressure-sensitive adhesive layer (X) and the print-printing layer (Z) was removed. The one was used as a test sample.
Then, according to JIS 7161:1994, using a universal material testing machine (manufactured by A&D Co., Ltd., product name “Tensilon RTG-1225”), a chuck distance of 100 mm and a pulling speed of 200 mm/min. The breaking strength, breaking elongation, yield strength, yield elongation and elastic modulus of the test sample in the MD direction were measured.
In addition, "MD direction" refers to the direction in which the composition was applied when forming the coating film in Examples 1 to 6 and Comparative Examples 2 and 3, and in Comparative Example 1, the base film used. Refers to the flow direction of the film-forming machine when producing.

<Adhesive strength>
The printing/printing pressure-sensitive adhesive sheets produced in Examples and Comparative Examples were cut into a size of 200 mm in length×25 mm in width.
Then, each release material on the pressure-sensitive adhesive layer (X) and the print-printing layer (Z) was removed, and the exposed surface of the pressure-sensitive adhesive layer (X) was exposed to an environment of 23° C. and 50% RH (relative humidity). Then, a stainless plate (SUS304, No. 360 polishing) was attached, and the plate was left standing in the same environment for 24 hours.
After standing still for 24 hours, the adhesive force of the printing/printing pressure-sensitive adhesive sheet was measured by a 180° peeling method based on JIS Z0237:2000 at a pulling speed of 300 mm/min.

<Curved surface followability>
The release film (1) on the print-printing layer (Z) of the print-printing pressure-sensitive adhesive sheets produced in the examples and comparative examples was removed, and the pressure-sensitive adhesive sheet (manufactured by Lintec Co., Ltd., product name “PET100 ( A) PL thin") was attached to the surface of the printing and printing layer (Z), and then cut into a size of 250 mm length×22 mm width.
Then, the release film (2) on the pressure-sensitive adhesive layer (X) was removed, and the surface of the pressure-sensitive adhesive layer (X) exposed was placed on a cylinder under an environment of 23° C. and 50% RH (relative humidity). It was attached to an adherend [diameter: φ10 mm, material: polypropylene (PP) and polyethylene (PE)]. Then, after standing still for 7 days in an environment of 23° C. and 50% RH (relative humidity), the amount of separation from the adherend was measured.

<Printability>
The print-adhesive sheets prepared in Examples and Comparative Examples were subjected to bar code reading evaluation according to JIS L0849 (2004) to evaluate printability.
Specifically, first, a print print produced in Examples and Comparative Examples using a thermal transfer printer (manufactured by Zebra Technologies, trade name "140XiIII") and a thermal transfer ribbon (manufactured by Dexerials, trade name "TR4070"). A bar code was printed on the adhesive sheet for use.
Thereafter, using a bar code reading/verifying device (RJS, trade name "INSPECTOR 3000"), according to ANSI (American National Standards Institute) X3.182 (1990) standard Bar Code Quality Guideline, a five-level evaluation (excellent A>B). >C>D>F Inferior) was evaluated by bar code reading.

<Falsification prevention>
The pressure-sensitive adhesive sheets for printing and printing prepared in Examples and Comparative Examples were cut into a size of 300 mm length×25 mm width to prepare evaluation samples. The release film (1) on the printed print layer (Z) of the evaluation sample was removed, and printing was performed on the printed print layer (Z) according to the above-described evaluation method of printability.
Then, the release film (2) on the pressure-sensitive adhesive layer (X) was removed, and the exposed surface of the pressure-sensitive adhesive layer (X) was exposed to a stainless steel plate (at 23° C. and 50% RH (relative humidity). SUS304, No. 360 polishing) was applied and left standing in the same environment for 24 hours.
After standing for 24 hours, it was peeled from the stainless steel plate by a 180° peeling method at a pulling speed of 300 mm/min based on JIS Z0237:2000.
Then, it was affixed to a stainless plate again, bar code readability was evaluated according to the above-mentioned printability evaluation method, and the tamperproof property of the print-printing pressure-sensitive adhesive sheet was evaluated according to the following criteria.
-A: The printed surface was deformed, and the bar code readability (5-level evaluation) deteriorated before and after peeling. (Excellent tamper resistance).
F: The printed surface was not deformed, and the bar code readability (5-level evaluation) did not change before and after peeling. (It is inferior in tamper resistance).

<Interfacial adhesion>
The printing/printing pressure-sensitive adhesive sheets produced in Examples and Comparative Examples were cut into a size of 50 mm in length×30 mm in width. And it evaluated based on JISK5600-5-6.
The interfacial adhesion between the substrate layer (Y) and the printed print layer (Z) was evaluated according to the following criteria.
-A: Classification according to JIS K5600-5-6 was "0 (best)".
B: Classification according to JIS K5600-5-6 was "1" to "4".
F: Classification according to JIS K5600-5-6 was "5 (worst)".

As shown in Table 2, the printing/printing pressure-sensitive adhesive sheets of Examples 1 to 6 were different from the printing/printing pressure-sensitive adhesive sheets of Comparative Examples 1 to 3 in terms of a base layer (Y) and a printing/printing layer (Z). Due to its high interfacial adhesion, peeling does not occur easily at the interface between the base material layer (Y) and the printed printing layer (Z) even when it is attached to a curved surface, and it is also excellent in punching workability and cutting suitability. Thought to be a thing.
Moreover, the adhesive sheets for printing and printing of Comparative Examples 1 to 3 have low interfacial adhesion between the base material layer (Y) and the printing and printing layer (Z), and when attached to a curved surface, It is considered that peeling may occur at the interface with the print layer (Z), and that punching workability and cutting workability may be adversely affected.
Furthermore, the pressure-sensitive adhesive sheet for printing and printing of Comparative Example 1 was inferior in both tamperproof property and curved surface conformability.

The pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention is useful as a pressure-sensitive adhesive sheet used for identification or decoration, coating masking, surface protection of a metal plate or the like, which is used in a place where curved surface followability is required. ..

1, 2 Adhesive sheet for printing and printing 10 Laminated body 11 Base material layer (Y)
12 Adhesive layer (X)
13 Printing and printing layer (Z)
141 Release material

Claims (17)

A pressure-sensitive adhesive sheet for printing and printing, comprising a laminate in which an adhesive layer (X), a base material layer (Y), and a printing and printing layer (Z) are laminated in this order,
The laminate is
A coating film (z′) made of a composition (z) containing a non-adhesive resin (z1) which is a material for forming a print/printing layer (Z);
A coating film (y′) composed of a composition (y) containing one or more non-adhesive resins (y1) selected from the group consisting of acrylic urethane-based resins and olefin-based resins, which are materials for forming the base material layer (Y) )When,
Is directly laminated in this order, and then at least the coating films (z′) and (y′) are simultaneously dried to form a laminate,
A pressure-sensitive adhesive sheet for printing and printing, wherein the pressure-sensitive adhesive layer (X) in the laminate is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin which is a material for forming the pressure-sensitive adhesive layer (X). The laminate is
The coating film (z'), the coating film (y'), and the coating film (x') composed of the composition (x) are directly laminated in this order, and then the coating film (z') and the coating film (y The pressure-sensitive adhesive sheet for printing and printing according to claim 1, which is formed by simultaneously drying') and the coating film (x'). The composition (z), the composition (y), and the composition (x) are simultaneously applied to form a coating film (z'), a coating film (y'), and a coating film (x'). The pressure-sensitive adhesive for printing and printing according to claim 2, which is formed by directly laminating the coating film (z'), the coating film (y') and the coating film (x') after directly laminating in this order. Sheet. The thickness ratio of the pressure-sensitive adhesive layer (X) with respect to the total thickness 100 of the base material layer (Y) and the print/printing layer (Z) is 20 to 110. Adhesive sheet for printing and printing. The pressure-sensitive adhesive sheet for printing and printing according to any one of claims 1 to 4, wherein the laminate has a thickness of 2 to 90 µm. The pressure-sensitive adhesive sheet for printing and printing according to any one of claims 1 to 5, wherein the base material layer (Y) has a thickness of 0.3 to 50.0 µm. The adhesive sheet for printing and printing according to any one of claims 1 to 6, wherein the adhesive resin contained in the composition (x) contains an acrylic resin. The pressure-sensitive adhesive sheet for printing and printing according to any one of claims 1 to 7, wherein the non-adhesive resin (y1) is a UV non-curable resin having no polymerizable functional group. The pressure-sensitive adhesive sheet for printing and printing according to any one of claims 1 to 8, wherein the base material layer (Y) is a non-stretched sheet material. The pressure-sensitive adhesive sheet for printing and printing according to any one of claims 1 to 9, wherein the non-adhesive resin (z1) is a polyester resin and/or a urethane-modified polyester resin. The adhesive sheet for printing and printing according to any one of claims 1 to 10, which has a breaking elongation of 100% or more. The adhesive sheet for printing and printing according to any one of claims 1 to 11, which has a breaking strength of 32 MPa or less. The adhesive sheet for printing and printing according to any one of claims 1 to 12, which has an elastic modulus of 500 MPa or less. A method for producing the pressure-sensitive adhesive sheet for printing and printing according to any one of claims 1 to 13,
A method for producing a pressure-sensitive adhesive sheet for printing and printing, which comprises the following steps (1A) and (2A).
Step (1A): a step of directly laminating a coating film (z') made of the composition (z) and a coating film (y') made of the composition (y) in this order.
-Step (2A): a step of simultaneously drying the coating film (z') and the coating film (y') to form the printed print layer (Z) and the base material layer (Y). The method for producing an adhesive sheet for printing and printing according to claim 14, which comprises the following steps (1B) and (2B).
Step (1B): a coating film (z') composed of the composition (z), a coating film (y') composed of the composition (y), and a coating film (x') composed of the composition (x). The process of directly laminating and forming in this order.
Step (2B): a step of drying the coating film (z'), the coating film (y'), and the coating film (x') at the same time to form the laminate. The method for producing a pressure-sensitive adhesive sheet for printing and printing according to claim 15, wherein the composition (z), the composition (y), and the composition (x) are simultaneously applied in the step (1B). The method for producing a pressure-sensitive adhesive sheet for printing and printing according to any one of claims 14 to 16, wherein the composition (z) and the composition (y) each independently contain a diluent solvent.