WO2018181108A1

WO2018181108A1 - Pressure-sensitive adhesive sheet for printing and production method for pressure-sensitive adhesive sheet for printing

Info

Publication number: WO2018181108A1
Application number: PCT/JP2018/012000
Authority: WO
Inventors: 晃司土渕; 高志阿久津; 揮一郎加藤
Original assignee: リンテック株式会社
Priority date: 2017-03-27
Filing date: 2018-03-26
Publication date: 2018-10-04
Also published as: JP2020094076A

Abstract

The present invention relates to: a pressure-sensitive adhesive sheet for printing which includes a layered object comprising a pressure-sensitive adhesive layer (X), a base layer (Y), and a printing layer (Z) that have been superposed in this order, wherein the layered object was formed by superposing a coating film (z') constituted of a composition (z) containing a nontacky resin (z1), which is a material for forming the printing layer (Z), directly on a coating film (y') constituted of a composition (y) containing one or more nontacky resins (y1), which are materials for forming the base layer (Y) and are selected from the group consisting of acrylic urethane resins and olefin resins, and thereafter drying at least the coating films (z') and (y') at the same time, and the pressure-sensitive adhesive layer (X) contained in the layered object is a layer formed from a composition (x) containing a tacky resin, which is a material for forming the pressure-sensitive adhesive layer (X); and a method for producing the pressure-sensitive adhesive sheet for printing.

Description

Adhesive sheet for printing and printing, and method for producing adhesive sheet for printing and printing

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

Various types of pressure-sensitive adhesive sheets for printing are mainly made of a resin base material. Generally, when the substrate of the pressure-sensitive adhesive sheet for printing is made of a resin, a printing layer is provided on the surface of the substrate in order to improve the adhesion with ink.
It is also known to provide a pressure-sensitive adhesive layer on the surface of the substrate opposite to the print-printing layer in order to attach the pressure-sensitive adhesive sheet for printing to an adherend.

For example, Patent Document 1 discloses a printing tape comprising a resin film having elasticity in at least one of a vertical direction, a horizontal direction, and an oblique direction, and having a recording surface formed on a rough surface. Is disclosed.
Further, Patent Document 2 includes an image receiving body in which a release layer and an image receiving layer are sequentially formed on one side of a sheet-like substrate, and an adhesive body in which an adhesive layer is formed on one side of a separator. (G / 15 mm), an image forming body is disclosed wherein the adhesion strength of the substrate is 40 to 80 g and the adhesion strength of the separator is 25 to 39 g.

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

By the way, in the conventional adhesive sheet for printing and printing, it adheres to the problem that the printing ink drops due to poor interfacial adhesion between the printing and printing layers and the adherend to be attached is a curved surface. There has been a problem that the body is lifted or peeled off.
In addition, for example, when the printing / printing adhesive sheet is used for a tamper-proof label or the like, for example, when the printing / printing adhesive sheet is peeled from the adherend, the base material layer is destroyed so that the tampering prevention effect is exhibited. In such a type, there is a possibility that the adherend is contaminated such that the adhesive or a part of the broken base material layer remains on the adherend.

An object of the present invention is to provide an adhesive sheet for printing that is excellent in interfacial adhesion, printing and printing, falsification prevention, and curved surface followability.

The inventors of the present invention have a pressure-sensitive adhesive layer (X) (hereinafter also simply referred to as “layer (X)”), a base material layer (Y) (hereinafter also simply referred to as “layer (Y)”), and printing. A pressure-sensitive adhesive sheet for printing with a laminate in which a printing layer (Z) (hereinafter, also simply referred to as “layer (Z)”) is laminated in this order, the laminate being a material for forming the layer (Z) The coating film (z ′) formed from the specific composition (z) and the coating film (y ′) formed from the specific composition (y) which is a material for forming the layer (Y) in this order. After the direct lamination, at least the coating film (z ′) and the coating film (y ′) were dried at the same time, and the pressure-sensitive adhesive layer (X) was formed from the specific composition (x). It has been found that the above problem can be solved by using a pressure-sensitive adhesive sheet for printing and printing, which is a layer.

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

According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet for printing and printing that is excellent in interfacial adhesion, printing and printing properties, falsification prevention properties, and curved surface following properties.

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

In the present invention, whether the target resin belongs to the “adhesive resin” or the “non-adhesive resin” is determined based on the following procedures (1) to (4).
・ Procedure (1): A test piece obtained by providing a resin layer having a thickness of 20 μm formed only from a target resin on a polyethylene terephthalate (PET) film having a thickness of 50 μm and cutting the test piece to a size of 300 mm length × 25 mm width Make it.
Procedure (2): In an environment of 23 ° C. and 50% RH (relative humidity), the exposed surface of the resin layer of the test piece was attached to a stainless steel plate (SUS304 No. 360 polishing). Let stand in the environment for 24 hours.
・ Procedure (3): After standing, in an environment of 23 ° C. and 50% RH (relative humidity), the adhesive strength was increased at a pulling speed of 300 mm / min by 180 ° peeling method based on JIS Z0237: 2000. taking measurement.
Procedure (4): If the measured adhesive strength is 0.1 N / 25 mm or more, the target resin is determined as an “adhesive resin”. On the other hand, if the measured adhesive strength is less than 0.1 N / 25 mm, the target resin is determined as a “non-adhesive resin”.

In the present invention, the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
Moreover, a mass average molecular weight (Mw) and a number average molecular weight (Mn) are the values of standard polystyrene conversion measured by a gel permeation chromatography (GPC) method, and are specifically based on the method as described in an Example. Measured value.

In the present invention, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
Moreover, about the preferable numerical range (for example, range of content etc.), the lower limit value and upper limit value which were described in steps can be combined independently, respectively. For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to 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” It is also possible to select, or simply select a range of “60 or less”.

[Adhesive sheet for printing]
The pressure-sensitive adhesive sheet for printing of the present invention is a pressure-sensitive adhesive sheet for printing and printing having 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, The laminate is a coating material (z ′) made of a composition (z) containing a non-adhesive resin (z1) that is a material for forming a printing layer (Z), and a material for forming a base material layer (Y). A coating film (y ′) made of a composition (y) containing at least one non-adhesive resin (y1) selected from the group consisting of a certain acrylic urethane series resin and olefin series resin was directly laminated in this order. Thereafter, it is a laminate formed by simultaneously drying at least the coating films (z ′) and (y ′), and the adhesive layer (X) in the laminate is a material for forming the adhesive layer (X). It is a pressure-sensitive adhesive sheet for printing, which is a layer formed from the composition (x) containing an adhesive resin.

FIG. 1 is a schematic cross-sectional view of a pressure-sensitive adhesive sheet for printing and showing a configuration example of the pressure-sensitive adhesive sheet for printing and printing according to the present invention.
For example, the pressure-sensitive adhesive sheet for printing and printing of the present invention has a pressure-sensitive adhesive layer (X) 12, a base material layer (Y) 11, and a printing and printing layer (like the pressure-sensitive adhesive sheet 1 for printing and printing shown in FIG. Examples 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 printing layer (Z) 13 are directly laminated in this order. The pressure-sensitive adhesive sheet for printing of the present invention is preferably such that the pressure-sensitive adhesive layer (X), the base material layer (Y), and the printing / printing layer (Z) are directly laminated in this order.
Here, the above-mentioned “direct lamination” means, for example, in the former case, two layers are in direct contact with each other without any other layer between the base material layer (Y) and the print printing layer (Z). In the latter case, the other is 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 refers to a configuration in which the pressure-sensitive adhesive layer (X) and the print printing layer (Z) are in direct contact with the base material layer (Y) independently without having a layer.
Further, the release material described later is not included in the configuration of the “laminate” of the pressure-sensitive adhesive sheet for printing of the present invention.

The pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention may have a configuration in which a release material is further provided 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 and printing in this aspect, as shown in FIG. 1B, the pressure-sensitive adhesive sheet 2 for printing and printing further having a release material 141 on the surface of the pressure-sensitive adhesive layer (X) 12 can be mentioned. .

In addition, as the pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention, a different forming material is formed on the adhesive surface of the pressure-sensitive adhesive layer (X) (on the surface opposite to the side in contact with the base material layer). It is good also as a structure which laminated | stacked the adhesive layer (X ') formed from the composition which is (not shown).
Moreover, as an adhesive sheet for printing and printing of one aspect of the present invention, an intermediate layer (M) formed from a composition which is a different forming material between the base material layer (Y) and the adhesive layer (X). It is good also as a structure which laminated | stacked (for example, primer layer) (not shown).
In other words, the pressure-sensitive adhesive sheet for printing and printing which is one aspect of the present invention is not limited to the sheet according to each aspect shown in FIG. 1 as long as the aspect described above is satisfied.

<Laminated body>
The laminated body which the adhesive sheet for printing printing of this invention has is a laminated body which laminated | stacked the adhesive layer (X), the base material layer (Y), and the printing printing layer (Z) in this order, and printing printing layer ( A coating film (z ′) composed 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 are forming materials of a base material layer (Y) After directly laminating a coating film (y ′) composed of a composition (y) containing at least one non-adhesive resin (y1) selected from the group consisting of in this order, at least a coating film (z ′) And (y ′) are dried simultaneously, and the adhesive layer (X) in the laminate is a layer formed from the composition (x) containing an adhesive resin.
The pressure-sensitive adhesive layer (X) is a layer formed from the composition (x) containing a pressure-sensitive adhesive resin. For example, the pressure-sensitive adhesive layer (X) may be one obtained by heating and melting and extrusion laminating on the base material layer (Y). The coating film (x ′) made of the composition (x) containing an adhesive resin may be applied on the base material layer (Y) later and dried. In addition, for example, the pressure-sensitive adhesive layer (X) is prepared by previously extruding or drying the coating film (x ′) and pasting the substrate layer (Y) directly or via another layer. It may be. The pressure-sensitive adhesive layer (X) is preferably a layer formed by drying a coating film (x ′) comprising the composition (x), more preferably a coating film (z ′) and a coating film (y ') At the same time dried and formed.
And more preferably, as the laminate, after directly coating the coating film (z ′), the coating film (y ′), and the coating film (x ′) made of the composition (x) in this order. The coating film (z ′), the coating film (y ′), and the coating film (x ′) are simultaneously dried.

More preferably, as the laminate, at least the composition (z) and the composition (y) are simultaneously applied, and the coating film (z ′), the coating film (y ′), and the composition ( The coating film (x ′) composed of x) is 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, it is difficult to form a dry film of a thin film on the surface of the coating film as compared with the case where each composition is applied sequentially. Excellent adhesion between the printing layer (Z) and the substrate layer (Y).
From the same viewpoint, more preferably, as the laminate, the composition (z), the composition (y), and the composition (x) are simultaneously applied, and the coating film (z ′), After the coating film (y ′) and the coating film (x ′) are directly laminated in this order, the coating film (z ′), the coating film (y ′), and the coating film (x ′) are simultaneously dried to form. It has been done. By applying the composition (z), the composition (y), and the composition (x) at the same time, a dry film of a thin film is formed on the surface of each coating film as compared with the case of sequentially applying each composition. Since it becomes difficult to be carried out, it is excellent in the adhesiveness between the obtained layers.

Conventionally, the pressure-sensitive adhesive sheet for printing and printing is manufactured by, for example, the following method (hereinafter also referred to as “conventional manufacturing method”).
・ On the release treatment surface of a release material such as a release film, a pressure-sensitive adhesive composition is applied to form a coating film, and the coating film is dried to form a pressure-sensitive adhesive layer. A base film is prepared by applying a composition for forming a print printing layer on the release treatment surface of the release material to form a coating film, drying the coating film to form a printing printing layer, Or the manufacturing method which has the process of affixing the adhesive layer and print printing layer which were formed on the peeling material, respectively on base material layer surface and back surfaces, such as a sheet | seat.
In the conventional manufacturing method, a preformed base material layer is used, and the pressure-sensitive adhesive layer and the print printing layer are formed in advance on the release treatment surface of the release film.
However, since the base material layer and the printing layer are separately formed in the adhesive sheet for printing with a base material obtained by the conventional manufacturing method, the base material layer and the printing and printing layer Low interfacial adhesion.

On the other hand, the laminate that the pressure-sensitive adhesive sheet for printing and printing of the present invention has is composed of a coating film (y ′) composed of the composition (y) that is a forming material of the base material layer (Y) and the printing and printing layer (Z). After directly laminating the coating film (z ′) made of the composition (z) as the forming material in this order, at least the coating film (y ′) and the coating film (z ′) are dried “simultaneously” to form. It has been done.
Since the laminate was formed as such, 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 general production method described above. It will be a thing.
This is a coating film (y ′) composed of the composition (y) which is a forming material of the base material layer (Y) and a coating film (z) which is a forming material of the printing and printing layer (Z) ( In the process of simultaneously drying z ′), a mixed layer of the coating film is formed in the vicinity of the interface, and the molecular chains of the resins contained in each composition are entangled, whereby the base material layer (Y) and the print printing layer (Z This is thought to be due to improved interfacial adhesion to
Furthermore, the base material layer (Y) of the pressure-sensitive adhesive sheet for printing of the present invention is formed by drying the coating film (y ′) comprising the composition (y) as described above. Unlike the base film or sheet used in the conventional manufacturing method, it is an unstretched sheet-like material. Therefore, the pressure-sensitive adhesive sheet for printing and printing of the present invention is significantly more flexible than the pressure-sensitive adhesive sheet for printing and printing obtained by the conventional manufacturing method.

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

Similarly, the laminate is formed by directly laminating a coating film (z ′), a coating film (y ′), and a coating film (x ′) composed of the composition (x) in this order, In the case where the film (z ′), the coating film (y ′) and the coating film (x ′) are formed by drying at the same time, the interfacial adhesion between the base material layer (Y) and the printing layer (Z). In addition, 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-described conventional production method.
This is because, for the same reason as described above, the coating film (y ′) composed of the composition (y) which is the forming material of the base material layer (Y) and the composition (the forming material of the pressure-sensitive adhesive layer (X)) ( In the process of simultaneously drying the coating film (x ′) consisting of x), a mixed layer of the coating film is formed in the vicinity of the interface, and the molecular chain of the adhesive resin and the non-adhesive resin (y1) contained in each other composition It is considered that the interfacial adhesion between the base material layer (Y) and the pressure-sensitive adhesive layer (X) is improved by the entanglement of the molecular chains.

In addition, in this invention, although the laminated body which the adhesive sheet for printing printing has is specified by the manufacturing method as mentioned above, the situation which must be specified by such a manufacturing method exists.
In other words, the cross section in the thickness direction cut in the direction perpendicular to the surface of the printed printing layer (Z) of the laminate is used to measure the interface between the base material layer (Y) and the printed printing layer (Z). As a method for determining whether or not the film is formed based on the method of the present invention from the viewpoint of subjective vision, for example, a method of measuring the surface roughness is conceivable. However, since the roughness of the interface is very small, it cannot be measured accurately, and the difference in the roughness state depending on the region to be observed is very large. Therefore, it is very difficult to evaluate with specific physical property values such as surface roughness.
Under such circumstances, in the present invention, the laminated body included in the pressure-sensitive adhesive sheet for printing is specified by the production 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 printing layer (Z), and the base material layer (Y) and the pressure-sensitive adhesive layer in the case where the coating film (x ′) is formed by drying simultaneously. The same applies to the relationship with (X).

In the present specification, the “coating film” is a film formed from a composition that is a forming material by a known coating method, and the residual ratio of volatile components such as a solvent contained in the film. It refers to those in a state of 10 to 100% by mass with respect to 100% by mass of the total amount of volatile components contained in the composition before coating.
That is, in this 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 is a lamination | stacking which removes a volatile component by drying simultaneously a coating film (y ') and a coating film (z') simultaneously, and has a base material layer (Y) and a printing printing layer (Z). The body is formed. Moreover, in the case of the above-mentioned preferable laminated body, a volatile component is removed by drying simultaneously three coating films, a coating film (x '), a coating film (y'), and a coating film (z '), and adhesion. The laminated body comprised from the agent layer (X), the base material layer (Y), and the printing printing layer (Z) is formed.

In addition, about the method of forming a coating film (x '), a coating film (y'), and a coating film (z '), and the drying conditions of the formed coating film, respectively, "The adhesive sheet for printing printing" mentioned later As described in the item “Manufacturing method”.

<< Adhesive layer (X) >>
The pressure-sensitive adhesive layer (X) is a layer formed from a composition (x) containing a pressure-sensitive adhesive resin.
As described above, the pressure-sensitive adhesive layer (X) may be a layer formed from the composition (x) containing the pressure-sensitive adhesive resin, but preferably the coating film (x ′) composed of the composition (x) is dried. More preferably, the layer 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 pressure-sensitive adhesive layer (X) contains a pressure-sensitive adhesive resin.
In addition, in 1 aspect of this invention, components other than adhesive resin contained in composition (x) can be suitably adjusted according to the use application of the adhesive sheet for printing printing of this invention.
For example, in one embodiment of the present invention, from the viewpoint of making a pressure-sensitive adhesive sheet for printing and printing with improved adhesive strength, the composition (x) may further contain a tackifier and / or a crosslinking agent. In addition, you may contain the additive for adhesives used for a dilution solvent and / or a general 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 even more 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 acrylic resins, urethane resins, polyisobutylene resins, and olefin resins that satisfy the adhesive force as the above-mentioned adhesive resins.
These adhesive resins may be used alone or in combination of two or more.
In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
Furthermore, 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 ultraviolet 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%, based on the total amount (100% by mass) of the active ingredients of the composition (x). .95% by mass, more preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, and 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 of the acrylic resin in the adhesive resin is preferably from 30 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, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.

Examples of acrylic resins that can be used as adhesive resins include polymers containing structural units derived from alkyl (meth) acrylates having linear or branched alkyl groups, and (meth) acrylates having a cyclic structure. Examples thereof include a polymer containing a derived structural unit.

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. .

As an acrylic resin used in one embodiment of the present invention, an acrylic polymer having a structural unit (a1) derived from alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”). (A0) is preferred, and the acrylic copolymer having the structural unit (a2) derived from the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) together with the structural unit (a1). (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, still more preferably 1 to 8, and still more preferably 4 to 6 from the viewpoint of improving adhesive properties. It is.
The alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched 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 include meth) acrylate and stearyl (meth) acrylate.
These monomers (a1 ′) may be used alone or in combination of two or more.
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 weight, more preferably based on the total structural unit (100% by weight) of the acrylic polymer (A0) or the acrylic copolymer (A1). It 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 possessed by the monomer (a2 ′) refers to a functional group that reacts with a crosslinking agent that may be contained in the composition (x) described later and can serve as a crosslinking starting point or a functional group having a crosslinking promoting effect. , 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.
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) ) And hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; and 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.
As the monomer (a2 ′), 2-hydroxyethyl (meth) acrylate is preferable.

The content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30%, based on the entire structural unit (100% by weight) of the acrylic copolymer (A1). % By mass, 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 another 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 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1). To 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.

As the monomer (a3 ′), for example, olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc. (Meth) acrylate; styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloyl mole Phosphorus, N- vinylpyrrolidone and the like.
As the monomer (a3 ′), vinyl acetate is preferable.

{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 examples of the urethane resin include a urethane prepolymer (UX) obtained by reacting a polyol and a polyvalent isocyanate compound.
The urethane prepolymer (UX) may be obtained by further subjecting to 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, and still more preferably 20,000 to 70,000.

Examples of the polyol used as a raw material for the urethane-based prepolymer (UX) include polyol compounds such as alkylene type polyols, polyether type polyols, polyester type polyols, polyester amide type polyols, polyester / polyether type polyols, and polycarbonate type polyols. Although it is mentioned, if it is a polyol, it will not specifically limit, Bifunctional diol and a trifunctional triol may be sufficient.
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 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, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
Among these alkylene diols, glycols having a mass average molecular weight (Mw) of 1,000 to 3,000 are preferred from the viewpoint of suppressing gelation when the reaction with a chain extender is performed.

Examples of the polyvalent isocyanate compound that is a raw material for the urethane prepolymer (UX) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 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 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'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanate) Methyl) cyclohexane and the like.
In addition, these polyisocyanate compounds may be a trimethylolpropane adduct modified product of the polyisocyanate, a burette modified product reacted with water, or an isocyanurate 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-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, at least one selected from HMDI, IPDI, and modified products thereof is 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 a value measured according to JIS K1603-1: 2007. % By mass.

As the chain extender, a compound having at least one of hydroxyl group and amino group, or a compound having at least three of hydroxyl group and amino group is preferable.

The compound having at least one of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
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;
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 bisphenol include bisphenol A and the like.
Examples of the aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.

Examples of the compound having at least three hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, 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;

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

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

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

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 structural unit composed of isobutylene is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass with respect to all the structural units (100% by mass) of the PIB resin. %.
These PIB-based resins may be used alone or in combination of two or more.

Moreover, when using PIB-type resin, it is preferable to use together PIB-type resin with a high mass average molecular weight (Mw) and PIB-type resin with a low mass average molecular weight (Mw).
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 It is preferable to use 10,000 to 250,000 PIB resin (p2) (hereinafter also referred to as “PIB resin (p2)”) in combination.
By using the PIB resin (p1) having a high mass average molecular weight (Mw), the durability and weather resistance of the pressure-sensitive adhesive layer to be formed can be improved, and the adhesive strength can also be improved.
Further, by using a PIB resin (p2) having a low mass average molecular weight (Mw), it can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately plasticized. The wettability of the pressure-sensitive adhesive layer to the adherend can be improved, and the physical properties of adhesive, flexibility and the like can be improved.

The mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, still more preferably 310,000 to 450,000, and even more preferably 320,000 to 400,000. It 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, and still more preferably 180,000 to 210,000. It 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 even more. The amount 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 said olefin resin may be used independently and may be used in combination of 2 or more type.
Specific examples of the olefin-based resin include polyethylenes 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- Copolymers of olefins, copolymers of propylene and other α-olefins, copolymers of ethylene, propylene and other α-olefins, copolymers of ethylene and other ethylenically unsaturated monomers Examples thereof include ethylene (vinyl-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) and the like.
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 embodiment of the present invention, the composition (x) preferably further contains a tackifier from the viewpoint of obtaining a pressure-sensitive adhesive sheet for printing and printing with improved adhesive strength.
Here, the “tackifier” is a component that assists in improving the adhesive strength of the adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is a distinction.
The weight average molecular weight (Mw) of the tackifier is preferably 400 to 10,000, more preferably 500 to 8,000, and still more preferably 800 to 5,000.

Examples of tackifiers 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, and terpene phenols. Terpene resins such as epoxy resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; styrene obtained by copolymerizing a styrene monomer such as α-methylstyrene or β-methylstyrene with an aliphatic monomer Hydrogenated styrene resins obtained by hydrogenating these styrene resins; C5 systems obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha Petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; indene and vinyl And C9 petroleum resins obtained by copolymerizing C9 fractions such as toluene and hydrogenated petroleum resins.
These tackifiers may be used alone or in combination of two or more different softening points and structures.

The softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and still more preferably 70 to 150 ° C.
In the present specification, the “softening point” of the tackifier means a value measured according to JIS K2531.
Moreover, when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.

The content of the tackifier in the composition (x) is preferably 0.01 to 65% by mass, more preferably 0. 0% with respect to the total amount (100% by mass) of the active ingredients in the composition (x). It is 05 to 55% by mass, more preferably 0.1 to 50% by mass, still more preferably 0.5 to 45% by mass, and still more preferably 1.0 to 40% by mass.

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

(Crosslinking agent)
In one embodiment of the present invention, the composition (x) further contains a crosslinking agent together with an adhesive resin having the above-described functional group such as an acrylic copolymer having the above-described structural units (a1) and (a2). It is preferable to do.
The said crosslinking agent reacts with the functional group which the said adhesive resin has, and bridge | crosslinks resin.

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

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

(Adhesive additive)
In one embodiment of the present invention, the composition (x) contains an additive for pressure-sensitive adhesives used for general pressure-sensitive adhesives other than the above-described tackifier and crosslinking agent within a range not impairing the effects of the present invention. You may do it.
Examples of the adhesive additive include an antioxidant, a softening agent (plasticizer), a rust inhibitor, a pigment, a dye, a retarder, a catalyst, and an ultraviolet absorber.
These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
When these pressure-sensitive adhesive additives are contained, the content of each pressure-sensitive adhesive additive is preferably independently 0.0001 to 20 parts by mass, more preferably 100 parts by mass of the adhesive resin. 0.001 to 10 parts by mass.

(Diluted solvent)
In one embodiment of the present invention, the composition (x) may contain water or an organic solvent as a diluent solvent together with the various active ingredients described above, and may be in the form of a solution.
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, and cyclohexane. Etc.
In addition, these dilution solvents may be used independently and may be used in combination of 2 or more type.

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

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

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

(Non-adhesive resin (y1))
Non-adhesive resin (y1) belongs to acrylic urethane type resin or olefin type resin.
When the non-adhesive resin (y1) is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and the block copolymer, random copolymer, and graft copolymer are not limited. Any of polymers may be used.
Furthermore, in one aspect of the present invention, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y), the print layer (Z), and the pressure-sensitive adhesive layer (X), the composition (y) includes the above-mentioned component. 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% with respect to the total amount (100% by mass) of the active ingredients in the composition (y). To 100% by mass, more preferably 80 to 98% by mass, and 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 resin 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.

An acrylic urethane resin (hereinafter also referred to as “acrylic urethane resin (I)”), which is a reaction product of an acrylic polyol compound and an isocyanate compound, has a main chain of the acrylic resin as a skeleton, and has a molecular structure between them. Has a chemical structure crosslinked and cured by urethane bonds.
Since the acrylic resin as the main chain is rich in rigidity, it is resistant to tensile stress and hardly stretched, and since it has a structural unit derived from an isocyanate compound rich in reactivity, it is contained in the printing layer (Z). Since it is excellent in adhesiveness with the adhesive resin (z1), it is thought that it can contribute to the improvement of interfacial adhesiveness with the layer (Z). Furthermore, since it is excellent also in adhesiveness with the adhesive resin contained in adhesive layer (X), it is thought that it can also contribute to the improvement of interface adhesiveness with 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, “acrylic urethane-based resin (II)”) has (meth) acrylic acid at both ends of the linear urethane prepolymer (UY), with the main chain of the linear urethane prepolymer (UY) as a skeleton. It has a structural unit derived from a vinyl compound (VY) containing an ester.
Since acrylic urethane resin (II) has a portion derived from linear urethane polymer (UY) between acrylic sites in the main chain skeleton, the distance between crosslinking points is longer than that of acrylic urethane resin (I). The molecular structure tends to be a two-dimensional structure (network structure).
Further, since the urethane prepolymer (UY) of the main chain is linear, the stretching effect is high when an external force is applied.
Furthermore, the side chain of the structural unit derived from the vinyl compound (VY) containing the (meth) acrylic acid ester is a non-adhesive resin (z1) in the printing / printing layer (Z) and an adhesive in the adhesive layer (X). It has a structure that is easily entangled with the conductive resin.
Therefore, by using an acrylic urethane resin (II) as a forming material for the base material layer (Y), improvement in interfacial adhesion with the printing layer (Z), and further with the adhesive layer (X) It is thought 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, and still more preferably 10,000 to 150,000.

In one embodiment of the present invention, the acrylic urethane-based resin (II) included in the composition (y) as the non-adhesive resin (y1) is preferably an acrylic urethane-based resin (II).
Hereinafter, the acrylic urethane resins (I) and (II) will be described.

{{Acrylic Urethane Resin (I)}}
The acrylic polyol compound used as a raw material for the acrylic urethane-based 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 number of carbon atoms of the alkyl group contained in the monomer (b1 ′) is preferably 1 to 12, more preferably 4 to 8, and still more 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 monomers as the monomer (a1 ′) described above.
In addition, a monomer (b1 ') may be used independently and may be used in combination of 2 or more type.
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 with respect to the total structural unit (100% by mass) of the acrylic copolymer (B1). %, More preferably 80 to 99.5% by mass.

Examples of the monomer (b2 ′) include the same hydroxyl group-containing monomers that can be selected as the monomer (a2 ′).
In addition, a monomer (b2 ') may be used independently and may be used in combination of 2 or more type.

The content of the structural unit (b2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30% by weight with respect to the total structural unit (100% by weight) of the acrylic copolymer (B1). %, And more preferably 0.5 to 20% by mass.

The acrylic copolymer (B1) may further have a structural unit (b3) derived from another 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 monomer (a2 ′), and the same monomers as the monomer (a3 ′).

In the acrylic copolymer (B1), the content of the structural units (b1) and (b2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (B1). To 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.

On the other hand, examples of the isocyanate compound used as the raw material for the acrylic urethane resin (I) include the same polyvalent isocyanate compounds used as the raw material for the urethane prepolymer (UX).
However, as an 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 resin (I), the ratio of the structural unit derived from the acrylic polyol compound to the structural unit derived from the isocyanate compound [acryl polyol compound / isocyanate compound] is preferably 10/90 by mass ratio. Is 90/90, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, and still more preferably 40/60 to 60/40.

{{Acrylic Urethane Resin (II)}}
Examples of the linear urethane prepolymer (UY) that is a raw material for the acrylic urethane resin (II) include a reaction product of a diol and a diisocyanate compound.
The said diol and diisocyanate compound may be used independently and may be used in combination of 2 or more type.
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, still more preferably 5,000 to 100,000, and even more preferably. It is 10,000 to 80,000, 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.
Of these diols, polycarbonate diols are preferred.

Examples of the diisocyanate compound constituting the linear urethane prepolymer (UY) include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. From the viewpoint of stretchability when an external force is applied, alicyclic Diisocyanate is preferred.
In addition, as a specific diisocyanate compound, what corresponds to a diisocyanate compound is mentioned among the compounds illustrated as a polyvalent isocyanate used as the raw material of the above-mentioned urethane type prepolymer (UX).

Further, the linear urethane prepolymer (UY) may be obtained by performing a chain extension reaction using a chain extender together with a diol and a diisocyanate compound.
Examples of the chain extender include the same chain extenders as those exemplified as the chain extender that can be used in the synthesis of the urethane prepolymer (UX).

In one embodiment 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), an NCO group at the end of a urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate And a method of reacting with.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

As a vinyl compound (VY) used as the raw material of acrylic urethane type resin (II), at least (meth) acrylic acid ester is included.
The (meth) acrylic acid ester is the same as that corresponding to the (meth) acrylic acid ester among the monomers (a1 ′) to (a3 ′) used as the raw material of the acrylic copolymer (A1). Things.
However, as the (meth) acrylic acid ester, at least one selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is preferable, and it is more preferable to use alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate together. preferable.

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

The number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
As the said alkyl (meth) acrylate, the same thing as what was illustrated as a monomer (a1 ') used as the raw material of the above-mentioned acrylic copolymer (A1) is mentioned.

Moreover, as hydroxyalkyl (meth) acrylate, the same thing as what was illustrated as hydroxyalkyl (meth) acrylate used in order to introduce an ethylenically unsaturated group into the both ends of the above-mentioned linear urethane prepolymer (UY) is mentioned. Is mentioned.

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

In one embodiment of the present invention, the content of (meth) acrylic acid ester in the vinyl compound (VY) used as the raw material for the acrylic urethane resin (II) is the total amount (100% by mass) of 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.

In one embodiment of the present invention, the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in vinyl compound (VY) used as a raw material for 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 with respect to the total amount (100% by mass).

The acrylic urethane resin (II) can be obtained by polymerizing a linear urethane prepolymer (UY) as a raw material and a vinyl compound (VY).
As a specific polymerization method, a radical generator is blended in an organic solvent together with the linear urethane prepolymer (UY) and vinyl compound (VY) as raw materials, and both ends of the linear urethane prepolymer (UY). It can be synthesized by a radical polymerization reaction of a vinyl compound (VY) starting from an ethylenically unsaturated group.
Examples of the radical generator 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 polymerization degree 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) to the structural unit derived from the vinyl compound (VY) [(UY) / (VY)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, still more preferably 35 / 65 to 55/45.

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

In one embodiment of the present invention, the olefinic resin may be a modified olefinic resin that has been further modified by one or more 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 polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride. Is mentioned.
Examples of the unsaturated carboxylic acid or its anhydride 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 anhydride, tetrahydrophthalic anhydride, and the like.
In addition, unsaturated carboxylic acid or its anhydride may be used independently, and may be used in combination of 2 or more type.

An acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification is a modification obtained by graft-polymerizing an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin that is a main chain. A polymer is 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 still more preferably 1 to 12.
As said alkyl (meth) acrylate, the same thing as the compound which can be selected as said monomer (a1 ') is mentioned, for example.

Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft-polymerizing a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin as the main chain.
Examples of the hydroxyl group-containing compound include the same hydroxyl group-containing monomers that can be selected as the 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, and even more preferably 50,000 to 300,000. is there.

(Resin other than acrylic urethane resin and olefin resin)
In one embodiment 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 naphthalate. Polyester resin such as phthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resin; polymethylpentene; polysulfone; polyetheretherketone; polyethersulfone; Sulfides; Polyimide resins such as polyetherimide and polyimide; Polyamide resins; Acrylic resins; Fluorine resins and the like.

However, the viewpoint of further improving the interfacial adhesion between the base material layer (Y) and the print printing layer (Z), and further the viewpoint of further improving the interfacial adhesiveness 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-based resin and the olefin-based resin in the composition (y) is small.
The specific content of the resin other than the acrylic urethane resin and the olefin resin is a non-adhesive resin (y1) selected from the group consisting of an acrylic urethane resin and an 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, and even more preferably less than 1 part by mass with respect to 100 parts by mass of the total amount of .

(Crosslinking agent)
In one aspect of the present invention, when the composition (y) contains an acrylic urethane resin, it is more preferable to further contain a crosslinking agent in order to crosslink the acrylic urethane resin.
As the said crosslinking agent, the isocyanate type compound as a crosslinking agent is preferable, for example.
As the isocyanate compound as the crosslinking agent, various isocyanate compounds can be used as long as they react with the functional group of the acrylic urethane resin to form a crosslinked structure.
The isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups per molecule.

Examples of the polyisocyanate compound 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, xylylene diisocyanate; dicyclohexylmethane-4,4-diisocyanate, bicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene Examples thereof include 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.
In addition, biuret bodies, isocyanurate bodies of these isocyanate compounds, adduct bodies that are reaction products of these isocyanate compounds with non-aromatic low-molecular active hydrogen-containing compounds such as ethylene glycol, trimethylolpropane, castor oil, etc. Modified products can also be used.

Of these isocyanate compounds, aliphatic isocyanate compounds are preferable, aliphatic diisocyanate compounds are more preferable, and pentamethylene diisocyanate, hexamethylene diisocyanate, and heptamethylene diisocyanate are still more preferable.
In the composition (y), the isocyanate compound may be used alone or in combination of two or more.

In the composition (y), the content ratio of the acrylic urethane resin and the isocyanate compound as a crosslinking agent is an isocyanate system as a crosslinking agent with respect to a total of 100 parts by mass of the acrylic urethane resin as a solid content ratio. The compound is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and still more preferably 3 to 15 parts by mass.

(catalyst)
In one embodiment of the present invention, when the composition (y) contains an acrylic urethane resin and the crosslinking agent, the composition (y) further preferably contains a catalyst together with the crosslinking agent.
As the catalyst, a metal catalyst is preferable, and a metal catalyst excluding a tin compound having a butyl group is more preferable.
Examples of the metal catalyst include a tin catalyst, a bismuth catalyst, a titanium catalyst, a vanadium catalyst, a zirconium catalyst, an aluminum catalyst, and a nickel 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 tin-based catalysts include tin organometallic compounds having structures such as alkoxides, carboxylates, chelates, etc., and preferably acetylacetone complexes, acetylacetonates, octylic acid compounds or naphthenes of these metals. An acid compound etc. are mentioned.
Similarly, the bismuth catalyst, titanium catalyst, vanadium catalyst, zirconium catalyst, aluminum catalyst, or nickel catalyst is an organometallic compound of bismuth, titanium, vanadium, zirconium, aluminum, or nickel, respectively. In addition, compounds having a structure such as alkoxide, carboxylate, chelate and the like can be mentioned, and preferred examples thereof include acetylacetone complexes, acetylacetonates, octylic acid compounds and naphthenic acid compounds of these metals.

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

As the tin-based catalyst, general formula RxSn (L) _(4-X) (wherein 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 It 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 having 5 to 25 carbon atoms, further preferably an alkyl group having 5 to 20 carbon atoms, and the aryl group of R is The number of carbon atoms is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable. When two or more R are present in one molecule, each R may be the same or different.
L is preferably an aliphatic carboxylic acid, aromatic carboxylic acid or aromatic sulfonic acid having 2 to 20 carbon atoms, 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 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 resin and the catalyst is preferably 0.001 to 5 parts by mass in terms of solid content of the catalyst with respect to 100 parts by mass in total of the acrylic urethane resin. The amount is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2 parts by mass.

(Substrate additive)
1 aspect of this invention WHEREIN: The composition (y) may contain the base material additive contained in the base material which a general adhesive sheet has in the range which does not impair the effect of this invention.
Examples of such base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants.
These base material additives may be used alone or in combination of two or more.
In the case of containing these base material additives, the content of each base material additive is preferably 0.0001 to 20 parts by mass with respect to 100 parts by mass of the non-adhesive resin (y1), More preferably, it is 0.001 to 10 parts by mass.

(Diluted solvent)
In one embodiment of the present invention, the composition (y) may contain water or an organic solvent as a diluent solvent together with the various active ingredients described above, and may be in the form of a solution.
Examples of the organic solvent include the same organic solvents used when the composition (x) is prepared in the form of a solution.
In addition, the dilution solvent contained in a composition (y) may be used independently, and may be used in combination of 2 or more type.

When the composition (y) is in the form of a solution containing a diluting solvent, the active ingredient concentration of the composition (y) is preferably independently 0.1 to 60% by mass, more preferably 0. It 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 elongation at break of the base material layer (Y) formed from the composition (y) is preferably 100% or more, more preferably 120% or more, still more preferably 200% or more, and still more preferably 350% or more. In addition, the upper limit of the elongation at break is not particularly limited, but is preferably 1,000% or less.
Moreover, 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.
In addition, the breaking elongation and breaking strength of the base material layer (Y) are the same as in the case of producing the pressure-sensitive adhesive sheet for printing and printing, and the coating film (y ′ ) Formed from the base material layer (Y). About the specific measuring method, it is the same as that of the measuring method of the breaking elongation and breaking strength of the adhesive sheet for printing printing described in an Example.

<< Printing 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 is made of the composition (y) described above. It was formed by drying simultaneously with the coating film (y ′).

[Composition (z)]
The composition (z), which is a material for forming the printing layer (Z), contains a non-adhesive resin (z1). The composition (z) may contain a resin other than the non-adhesive resin (z1) as long as the effects of the present invention are not impaired. You may contain the additive contained.

(Non-adhesive resin (z1))
The non-adhesive resin (z1) is a non-adhesive resin different from the aforementioned non-adhesive resin (y1), preferably a polyester-based resin and / or a urethane-modified polyester-based resin, more preferably a urethane-modified resin. It is a polyester resin.
When the non-adhesive resin (z1) is a copolymer having two or more structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and Any of the graft copolymers may be used.
In one embodiment of the present invention, a resin included in a general print printing layer other than a polyester-based resin and a urethane-modified polyester-based resin is used as the non-adhesive resin (z1) as long as the effects of the present invention are not impaired. You may contain.

The content of the non-adhesive resin (z1) in the composition (z) is preferably 50 to 100% by mass, more preferably 65% with respect to 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, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
Moreover, as a total content rate of the polyester-type resin and / or urethane-modified polyester-type resin in non-adhesive resin (z1), the whole quantity (100 mass%) of non-adhesive resin (z1) contained in a composition (z) ) Is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and 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 between 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. For example, terephthalic acid, phthalic acid, sulfoterephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid. Acids, aromatic dicarboxylic acids such as 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 Alicyclic dicarboxylic acids such as their anhydrides or esters; and the like.

Examples of the diol component or polyol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 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 such as 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like; p-xylene glycol, bisphenol A and the like Good Family glycol; and the like.
Examples of the urethane polyester resin that can be used as the non-adhesive resin (z1) include those having a urethane bond in addition to the polyester 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 a polyisocyanate compound, the thing similar to the polyisocyanate compound mentioned above as an isocyanate type compound as a crosslinking agent which a composition (y) may contain can be used. The polyisocyanate compound used for 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 an aromatic polyester. The basic structure of the aromatic polyester is one having a repeating unit derived from an aromatic compound in the main-chain polyester structure. For example, one or both of a dicarboxylic acid and a glycol compound which are part or all of a copolymer raw material Is obtained when is an aromatic compound.

As the non-adhesive resin (z1), a polyester resin or a urethane-modified polyester resin may be used alone, or two or more selected from the group consisting of a polyester resin and a urethane-modified polyester resin are combined. May be used.
As the non-adhesive resin (z1), it is more preferable to include two types of resins having different glass transition points, and it is more preferable to include two types of urethane-modified polyester resins having different glass transition points.

When the composition (z) includes two types of resins having different glass transition points as the non-adhesive resin (z1), the difference between the glass transition points of each resin is preferably 20 ° C. or more, more preferably 30 ° C. As mentioned above, More preferably, it is 50 degreeC or more, More preferably, it is 70 degreeC or more.
In this case, the glass transition point of the resin having a relatively higher glass transition point is preferably 40 to 105 ° C., more preferably 50 to 100 ° C., and still more preferably 70 to 95 ° C.
The glass transition point of the resin having a relatively lower glass transition point is preferably −30 to 15 ° C., more preferably −25 to 5 ° C.
When the composition (z) contains two types 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 in the glass transition point. The amount is preferably 1 to 50 parts by weight, more preferably 10 to 45 parts by weight, and still more preferably 15 to 40 parts by weight with respect to a total of 100 parts by weight 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 a 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, more preferably 10,000 to 60,000.

(Crosslinking agent)
More preferably, the composition (z), which is a material for forming the printing layer (Z), 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 a crosslinking agent that may be contained in the composition (y), and the preferred embodiment thereof is also the same.
In the composition (z), the isocyanate compound may be used alone or in combination of two or more. In the composition (z), the polyester resin and / or the urethane-modified polyester resin. And the content ratio of the isocyanate compound as the crosslinking agent is preferably 1 as the isocyanate compound as the crosslinking agent with respect to a total of 100 parts by mass of the polyester resin and / or the urethane-modified polyester resin as a solid content ratio. -30 parts by mass, more preferably 2-20 parts by mass, still more preferably 3-15 parts by mass.

(catalyst)
It is more preferable that the composition (z), which is a material for forming the printing layer (Z), further 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 those similar to the catalyst that may be contained in the composition (y) described above, and the preferred embodiments thereof are also the same.

In the composition (z), the said catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.
In the composition (z), the content of the polyester resin and / or the urethane-modified polyester resin and the catalyst is such that the catalyst is solid relative to a total of 100 parts by mass of the polyester resin and / or the urethane-modified polyester resin. The amount is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and still more preferably 0.1 to 2 parts by mass.
Further, when a metal catalyst is used as the catalyst, the metal catalyst is preferably 0.001 to 5 parts by mass in terms of metal amount with respect to a total of 100 parts by mass of the polyester resin and / or the urethane-modified polyester resin. The amount is more preferably 0.005 to 2 parts by mass, still more preferably 0.01 to 1 part by mass.

(Diluted solvent)
In one embodiment of the present invention, the composition (z) may contain water or an organic solvent as a diluent solvent together with the various active ingredients described above, and may be in the form of a solution.
Examples of the organic solvent include the same organic solvents used when the composition (x) is prepared in the form of a solution.
In addition, the dilution solvent contained in a composition (z) may be used independently, and may be used in combination of 2 or more type.

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

In one embodiment of the present invention, the composition (z) can be blended with various fillers such as an organic filler and an inorganic filler in order to improve slipperiness and obtain a matte feeling.
Examples of the organic filler include resin powder such as polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, acrylic resin such as methyl methacrylate, or 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 amount of the filler is preferably based on 100 parts by mass of the total amount of the non-adhesive resin (z1) and / or the aforementioned 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 pressure-sensitive adhesive sheet for printing>
The thickness of the laminate of the pressure-sensitive adhesive sheet for printing and printing according to one embodiment of the present invention is preferably 2 to 90 μm, more preferably 5 to 80 μm, still more preferably 10 to 70 μm, and 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, and 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 still more preferably 5.0. It is ˜30.0 μm, 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, and still more preferably 0.4. -5.0 μm.

In the present specification, the thickness of the laminate is a value measured using a constant pressure thickness measuring instrument based on JIS K6783, Z1702, and Z1709, and specifically measured based on the method described in the examples. Means the value.
The thickness of each layer constituting the laminate may be measured by the same method as the thickness of the laminate described above. For example, a cross section of the laminate cut in the thickness direction is observed with a scanning electron microscope. Then, the ratio of the thickness of each layer may be measured and calculated from the thickness of the laminate measured by the method described above.

In the pressure-sensitive adhesive sheet for printing according to 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 / printing layer (Z) is preferably 20 to 110, more preferably 20 to 100, still more preferably 23 to 98, still more preferably 25 to 95, and still more preferably 28 to 90.

In addition, as for the said laminated body which the adhesive sheet for printing printing of this invention has as mentioned above, a mixed layer arises between two coating films in the drying process of a coating film, and a printing printing layer (Z) and a base material layer (Y) 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 the two coating films and between the formed layers, for example, as described above, the cross section of the laminate cut in the thickness direction is observed with a scanning electron microscope to determine the thickness of each layer. When the thickness ratio is measured, and a mixed layer is formed between the printing layer (Z) and the base material layer (Y), it passes through an intermediate point in the thickness direction of the mixed layer. Further, the thickness ratio of each layer may be measured on the assumption that an interface exists on a surface parallel to the surface opposite to the substrate layer (Y) of the print printing layer (Z).

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

The pressure-sensitive adhesive force on the adhesive surface of the pressure-sensitive adhesive layer (X) of the pressure-sensitive adhesive sheet for printing according to one embodiment of the present invention is preferably 3.0 N / 25 mm or more, more preferably 4.0 N / 25 mm or more, and still more preferably 5 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 embodiment 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, still more preferably. Is 32 MPa or less.
The elongation at break of the pressure-sensitive adhesive sheet for printing of one embodiment of the present invention is preferably 100% or more, more preferably 150% or more, still more preferably 200% or more, and 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, still more preferably 50 MPa or less, and still more preferably 25 MPa or less.
The yield elongation of the pressure-sensitive adhesive sheet for printing and printing according to one embodiment of the present invention is preferably 3.0% or more, more preferably 4.0% or more, still more preferably 4.5% or more, and still more preferably 4 .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, and 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 embodiment of the present invention is preferably 1.0 MPa or more, more preferably 5.0 MPa or more, still more preferably 10 MPa or more, and still more preferably 25 MPa or more. And, Preferably it is 500 MPa or less, More preferably, it is 450 MPa or less, More preferably, it is 400 MPa or less.
In addition, the value of the said breaking strength, breaking elongation, yield strength, yield elongation, and elastic modulus means the value measured by the method as described in an Example.

<Release material>
The pressure-sensitive adhesive sheet for printing and printing according to one aspect of the present invention includes a surface of the pressure-sensitive adhesive layer (X) opposite to the base material layer (Y) and / or the base material layer (Y) of the printing and printing layer (Z). May further have a release material on the opposite surface.
In the case where a release material is used for any of the surfaces of the pressure-sensitive adhesive layer (X) and the printing / printing layer (Z), 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 process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release material coated on a release material substrate.

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

Examples of the release agent include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as 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, still more preferably 30 to 125 μm, and still more preferably 35 to 80 μm.

[Method for producing pressure-sensitive adhesive sheet for printing]
The method for producing the pressure-sensitive adhesive sheet for printing of the present invention is preferably a method having the following steps (1A) and (2A).
In addition, the method for producing a printing and printing pressure-sensitive adhesive sheet of the present invention can improve the productivity because the number of steps for producing the printing and printing pressure-sensitive adhesive sheet 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.
-Process (2A): The process of drying a coating film (z ') and a coating film (y') simultaneously, and forming a printing printing layer (Z) and a base material layer (Y).
Hereinafter, steps (1A) and (2A) will be described.

<Process (1A)>
In the step (1A), as a method for forming the coating film (z ′) and the coating film (y ′), for example, after forming the coating film (z ′), the coating film (y ′) is formed on the coating film (z ′). ') May be sequentially formed, but from the viewpoint of productivity, the composition (z) and the composition (y) are simultaneously applied, and the coating film (z') and the coating film (y ') are formed. The method of forming simultaneously is preferable.
In addition, from the viewpoint of handleability, the coating film (z ′) or the coating film (y ′) is preferably formed on the release treatment surface of the release material.
In addition, when a coating film (z ′) is formed on the release agent and at least the coating film (y ′) contains a diluting solvent, the coating film (z ′) is removed from the surface of the release material from the viewpoint of productivity. More preferably, the coating film (y ′) is formed on the coating film (z ′).
In other words, when each coating film is dried, each coating film is such that the gas derived from the diluted solvent generated from the coating film (y ′) is released into the air without passing through the coating film (z ′). It is more preferable to form By doing so, it can prevent that the evaporation or volatilization of the said dilution solvent is prevented by the coating film (z ') and printing printing layer (Z) with comparatively low gas permeability. As a result, poor drying of each coating film can be prevented, and productivity can be further improved.

As the coater used for applying 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, Examples include knife coaters, roll coaters, knife roll coaters, blade coaters, gravure coaters, curtain coaters, and die coaters.

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, a multilayer die coater is preferable from the viewpoint of operability.

In addition, it is preferable that a composition (z) and a composition (y) contain a dilution solvent each independently further from a viewpoint of making each coating film easy to form and improving productivity.
As the diluting solvent, the diluting solvent described above in the column of the pressure-sensitive adhesive sheet for printing can be used.
Moreover, the active ingredient density | concentration of the solution obtained by mix | blending a dilution solvent with each composition is as having mentioned above in the column of the adhesive sheet for 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 , 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 , still more preferably 10.0 to 100 g / m ² , and still more preferably. It is 20.0 to 95.0 g / m ² , 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 ) 100 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, even more preferably 4 to 20, and still more preferably 5 to 15.

In addition, in this process (1A), after forming the coating film of 1 layer or more of a coating film (z ') and a coating film (y'), before the process (2A) mentioned later, the hardening reaction of the said coating film is carried out. You may give the predrying process of the grade which does not advance.
For example, a pre-drying treatment may be performed each time the coating film (z ′) and the coating film (y ′) are formed, and the coating film (z ′) and the coating film (y ′) 2 After forming the coating film of the layers, the two layers may be subjected to pre-drying treatment at the same time. When pre-drying is performed, from the viewpoint of improving the interfacial adhesion between the printing layer (Z) and the base material layer (Y), two layers of the coating film (z ′) and the coating film (y ′) are used. It is preferable to pre-dry the two layers simultaneously after forming the coating film.
In this step (1A), the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not cure, but preferably in step (2A). Below the drying temperature.
The specific drying temperature indicated by the phrase “below the drying temperature in step (2A)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.

<Process (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. By curing, it is considered that the interfacial adhesion between the printing layer (Z) and the base material layer (Y) is improved.

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

The method having 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 one obtained by extrusion lamination on the surface opposite to the printing layer, and a coating film (x ′) made of the composition (x) containing an adhesive resin is 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 prepared by previously extruding or drying the coating film (x ′) and pasting the substrate layer (Y) directly or via another layer. It may be.

When using the method of forming a coating film (x '), the method of the following process (3A) or (3A') is mentioned, for example.
Step (3A): A composition (x) containing an adhesive resin is applied on the surface of the base material layer (Y) obtained in the step (2A) on the side opposite to the printing layer (Z). The process of forming a coating film (x ') and drying the coating film and forming an adhesive layer (Y).
Step (3A ′): A composition (x) containing an adhesive resin is applied to the release treatment 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 prepared on the release material on the surface opposite to the printed printing layer (Z) of the base material layer (Y) obtained in the step (2A) was prepared. A step of attaching the layer (X).
Examples of the method for forming the coating film (x ′) include spin coater, spray coater, bar coater, knife coater, roll coater, knife roll coater, blade coater, gravure coater, curtain coater, and die coater. .
Moreover, 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 aforementioned dilution solvent. Moreover, the active ingredient density | concentration of the solution obtained by mix | blending a dilution solvent with a composition (x) is also as above-mentioned.

The coating amount of the coating film (x ') is preferably 0.1 ~ 100.0g / ^{m 2,} more preferably 0.5 ~ 80.0g / ^{m 2,} more preferably 1.0 ~ 70.0 g / m 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, and 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., and still more preferably 90 to 135 ° C. is there.

Further, before providing the pressure-sensitive adhesive layer (X) in the step (3A) or (3A ′), an intermediate layer (M) is further provided on the base material layer (Y), and the intermediate layer ( The pressure-sensitive adhesive layer (X) may be provided on the surface opposite to the base material layer (Y) of M) using 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 is compatible with both the non-adhesive resin (y1) that forms the base layer (Y) and the adhesive resin that forms the adhesive layer (X). Examples include a primer layer formed from a resin.

The pressure-sensitive adhesive layer (X) is preferably formed by drying the coating film (x ′) composed of the composition (x), more preferably the coating film (z ′). And the coating film (y ′) and the coating film (x ′) are dried and formed simultaneously.
Therefore, the method for producing the 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 ′) comprising the composition (z), a coating film (y ′) comprising the composition (y), and a coating film (x ′) comprising the composition (x) A process of directly stacking layers in this order.
-Process (2B): The process of drying a coating film (z '), a coating film (y'), and a coating film (x ') simultaneously, and forming the said laminated body.
Hereinafter, steps (1B) and (2B) will be described.

<Process (1B)>
In the step (1B), as a method for forming the coating film (z ′), the coating film (y ′), and the coating film (x ′), for example, after forming the coating film (z ′), the coating film (z A sequential formation method may be used, in which a coating film (y ′) is formed on the coating film (y ′) and a coating film (x ′) is formed on the coating film (y ′). From the viewpoint of productivity, the composition ( A method of simultaneously applying z), the composition (y), and the composition (z) to form the coating film (z ′), the coating film (y ′), and the coating film (x ′) is preferable.
In addition, it is preferable to form a coating film (z ') on the peeling process surface of a peeling material from a viewpoint of handleability and productivity.
Further, when a coating film (z ′) is formed on the release agent and at least the coating film (y ′) or the coating film (x ′) contains a diluent solvent, the release material, the coating film ( More preferably, z ′), the coating film (y ′), and the coating film (x ′) are formed in this order.
That is, when each coating film is dried, the gas derived from the dilution solvent generated from the coating film (y ′) and / or the coating film (x ′) does not pass through the coating film (z ′) in the air. It is more preferable to form each coating film so as to be released. As described above in the description of the step (1A), it is possible to prevent the evaporation or volatilization of the diluting solvent from being hindered by the coating film (z ′) and the printing layer (Z) having relatively low gas permeability. As a result, poor drying of each coating film can be prevented, and productivity can be further improved.

As a coater used when forming each coating film sequentially, each coater mentioned above etc. are mentioned, for example.
Moreover, as a coater used when apply | coating a composition (z), a composition (y), and a composition (x) simultaneously, the multilayer coater which can apply | coat at least 3 layers simultaneously is mentioned. Specifically, a multilayer curtain coater, a multilayer die coater, etc. are mentioned. Among these, from the viewpoint of operability, a multilayer die coater capable of simultaneously applying three or more layers is preferable.

In addition, from the viewpoint of facilitating formation of each coating film and improving productivity, the composition (x), the composition (y), and the composition (z) each independently further contain a dilution solvent. Is preferred.
As the diluting solvent, the diluting solvent described above in the column of the pressure-sensitive adhesive sheet for printing can be used.
Moreover, the active ingredient density | concentration of the solution obtained by mix | blending a dilution solvent with each composition is as having mentioned above in the column of the adhesive sheet for printing.
Moreover, the suitable application quantity of a coating film (z '), a coating film (y'), and a coating film (x ') is as above-mentioned, respectively.

Coating (z '), the coating (y'), and film (x ') the total coating amount of relative ^(g / m 2) 100, the coating film (y' coating amount of) of (g / ^{m 2)} The ratio is preferably 10 to 95, more preferably 20 to 90, still more preferably 30 to 80, and 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, and 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 process (1B), after forming the coating film of 1 layer or more of a coating film (z '), a coating film (y'), and a coating film (x '), before the process (2B), the said You may perform the predrying process of the grade which does not advance the hardening reaction of a coating film.
For example, the pre-drying treatment may be performed each time the coating film (z ′), the coating film (y ′), and the coating film (x ′) are formed. After forming the two-layer coating film of the coating film (y ′), the two layers may be pre-dried at the same time, and the coating film (z ′), coating film (y ′) and coating film (x ′). After the three-layer coating film is formed, the three layers may be pre-dried simultaneously. When pre-drying is performed, from the viewpoint of improving the interfacial adhesion between the printing layer (Z) and the base material layer (Y), two layers of the coating film (z ′) and the coating film (y ′) are used. It is preferable to pre-dry the two layers simultaneously after forming the coating film. From the viewpoint of improving the interfacial adhesion between the printing 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), the coating film It is more preferable to pre-dry the three layers at the same time after forming a three-layer coating film of (z ′), coating film (y ′) and coating film (x ′).
In the present step (1B), the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not proceed, but preferably in the step (2B). Below the drying temperature.
The specific drying temperature indicated by the phrase “below the drying temperature in step (2B)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.

<Process (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 is formed 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 ′). 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 in a state where the adhesive resin and / or the non-adhesive resin are intertwined with each other. It is considered that the interfacial 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, still more preferably 80 to 140 ° C, and still more preferably 90 to 135 ° C.

Moreover, when the adhesive sheet for printing and printing of 1 aspect of this invention is a structure further equipped with the 2nd adhesive layer (X2) other than adhesive layer (X) on the surface of an adhesive layer (X), it is adhesive. The second pressure-sensitive adhesive layer (X2) other than the agent layer (X) may be separately formed and adhered 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 that is a forming material of the second pressure-sensitive adhesive layer (X2) on the adhesive surface of the pressure-sensitive adhesive layer (X) of the laminate after forming the laminated body. The coated film may be formed by drying, and the second pressure-sensitive adhesive layer (X2) formed on the release-treated surface of a separately prepared release material is applied on the adhesive surface of the pressure-sensitive adhesive layer (X). It may be formed.

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

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

<Measurement of glass transition point>
Based on JIS K7121, it measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (The product made by TI Instruments Japan Co., Ltd., product name "DSC Q2000").

<Thickness of laminate>
It was measured using a constant pressure thickness measuring instrument (model number: “PG-02J”, standard: conforming to JIS K6783, Z1702, Z1709) manufactured by Teclock Co., Ltd.
Specifically, after measuring the total thickness of the pressure-sensitive adhesive sheet for printing and printing to be measured, a value obtained by subtracting the thickness of the release material measured in advance was defined as “the thickness of the laminate”.

<Thickness of each layer>
Each release material on the pressure-sensitive adhesive layer (X) and the print-printing layer (Z) of the pressure-sensitive adhesive sheet for printing and printing produced in Examples and Comparative Examples was removed, and polyethylene was formed on the surface of the pressure-sensitive adhesive layer (X) exposed. A terephthalate (PET) film (manufactured by Mitsubishi Plastics, trade name “Diafoil T-100”, thickness 50 μm) was bonded to obtain a measurement sample.
A cross section in the thickness direction of the measurement sample cut in the direction perpendicular to the surface of the printed printing layer (Z) was observed using a scanning electron microscope (product name “S-4700” manufactured by Hitachi, Ltd.). And the pressure-sensitive adhesive layer (X), the base material layer (Y), and the print printing layer (Z) with respect to 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.
And based on the thickness ratio of each layer, the thickness of each layer was computed from the actual value of the "thickness of a laminated body" measured by the above-mentioned method.

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 Acrylic copolymer having a structural unit derived from a raw material monomer consisting of 0.0 / 1.0 (mass ratio), mass average molecular weight (Mw): 1,000,000, diluting solvent: ethyl acetate, solid content concentration: 15% by mass ) 100 parts by mass (solid content ratio) and 25 parts by mass (solid content ratio) of rosin resin (Arakawa Chemical Industries, product name “KE-359”, softening point: 94 to 104 ° C.) as a tackifier ), And 1.62 parts by mass (solid content ratio) of an isocyanate-based crosslinking agent (product name “Takenate D-110N”, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent, mixed and mixed uniformly Thus, a composition (x) having a solid content concentration (active ingredient concentration) of 40% by mass was prepared.

Production Example 2
(Preparation of composition (ya))
Non-adhesive resin (y1), an acid-modified olefin-based resin solution (Mitsui Chemicals, product name “Unistal H-200”, mass average molecular weight (Mw): 145,000, glass transition point: −53 ° C., diluting solvent: mixed solvent of methylcyclohexane and methyl ethyl ketone, solid content concentration (active ingredient concentration): 20% by mass) was used as the composition (ya).

Production Example 3
(Preparation of composition (yb))
(1) Synthesis of linear urethane prepolymer (UY) In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate is added to 100 parts by mass (solid content ratio) of polycarbonate diol having a mass average molecular weight (Mw) of 1,000. Blended so that the equivalent ratio of the hydroxyl group of polycarbonate diol to the isocyanate group of isophorone diisocyanate is 1/1, 160 parts by mass of toluene is further added, and the isocyanate group concentration is theoretical while stirring the mixture in a nitrogen atmosphere. The reaction was allowed to proceed for 6 hours or more at 80 ° C. until the amount was reached.
Subsequently, 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 is added, and further at 80 ° C. until the isocyanate groups at both ends disappear. The mixture was reacted 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-based resin (II) In a reaction vessel under a nitrogen atmosphere, 100 parts by mass (solid content ratio) of linear urethane prepolymer (UY) obtained in (1) above, methyl methacrylate (MMA) 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 The mixture was heated to 105 ° C. with stirring.
In the meantime, a solution obtained by further diluting 2.2 parts by mass (solid content ratio) of radical initiator (manufactured by Nippon Finechem Co., Ltd., product name “ABN-E”) with 210 parts by mass of toluene was added to the reaction vessel. It was added dropwise over 4 hours while maintaining the temperature.
After completion of the dropwise addition of the solution, a 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 (yb) To 100 parts by mass (solid content ratio) of the acrylic urethane resin (II) obtained in (2), which is a non-adhesive resin (y1), a crosslinking agent 6.3 parts by mass (solid content ratio) of hexamethylene diisocyanate-based cross-linking agent (product name “Coronate HL” manufactured by Tosoh Corporation), and dioctyltin bis (2-ethylhexanoate) 1.4 as a catalyst A part by mass (solid content ratio) was 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))
70 parts by mass of non-adhesive resin (z1), urethane-modified polyester resin having a basic structure of an aromatic polyester (manufactured by Toyobo Co., Ltd., product name “Byron UR1700”, number average molecular weight 16,000, glass transition point 92 ° C.) And 30 parts by mass (non-adhesive resin) of urethane-modified polyester resin having a basic structure of aromatic polyester (manufactured by Toyobo Co., Ltd., product name “Byron UR8700”, number average molecular weight 32,000, glass transition point −22 ° C.) (100 parts by mass as (z1)), 3 parts by mass of a hexamethylene diisocyanate-based crosslinking agent (manufactured by Tosoh Corporation, product name “Coronate HL”) as a crosslinking agent, and a bismuth catalyst (manufactured by Nippon Chemical Industry Co., Ltd., product) Name "Pucat 25", 25% by mass in terms of bismuth) 0.30 parts by mass, and solvent Then, a mixed solvent composed of toluene, methyl ethyl ketone and cyclohexanone (mass ratio: toluene: methyl ethyl ketone: cyclohexanone = 10: 10: 1) is mixed and stirred uniformly to obtain a solid content concentration (active ingredient concentration) of 25% by mass. A composition (z) 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 Corporation, product name “SP-PET 381031”, polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm.
Release film (2): manufactured by Lintec Corporation, product name “SP-PET 382150”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm.
-Base film: manufactured by Toray Industries, Inc., product name “Lumirror 25T61M”, biaxially stretched polyester (PET) film, thickness: 25 μm.

Example 1
(1) Formation of coating film Using an applicator, a coating film (z ′) made of the composition (z) prepared in Production Example 4 is formed on the release agent layer of the release film (1) as a release material. The coating film (y ′) comprising the composition (ya) prepared in Production Example 2 on the coating film (z), and the composition prepared in Production Example 1 on the coating film (y ′) ( A coating film (x ′) consisting of x) was sequentially formed.
In addition, 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 and each layer of the laminate described in Table 1. It adjusted so that it might become the thickness of.
(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 form a release agent layer of the release film (1). In this order, a laminated body in which the layer (Z), the layer (Y), and the layer (X) were directly laminated was formed.
And the release agent layer of the peeling film (2) prepared separately from the peeling film on the layer (Z) was laminated | stacked on the surface of the layer (X) exposed, and the adhesive sheet for printing printing was obtained.

Example 2
(1) Formation of coating film On the release agent layer of the release film (1) as 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 applied in this order at a coating speed of 30 m / min using a multilayer die coater (width: 250 mm), and the coating film (z ′) and coating film (y ') And the coating film (x') were simultaneously formed in this order.
In addition, the application 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, and the release agent layer of the release film (1). In this order, a laminated body in which the layer (Z), the layer (Y), and the layer (X) were directly laminated was formed.
And the release agent layer of the peeling film (2) prepared separately from the peeling film on the layer (Z) was laminated | stacked on the surface of the layer (X) exposed, and the adhesive sheet for printing printing was obtained.

Example 3
Except having changed the coating amount of each composition for forming a coating film (z '), a coating film (y'), and a coating film (x ') into the quantity of Table 1, respectively, Example Using the same method as in No. 2, a pressure-sensitive adhesive sheet for printing was obtained.

Examples 4 and 5
The composition (yb) prepared in Production Example 3 was used in place of the composition (ya), and the coating film (z ′), coating film (y ′), and coating film (x ′) ) The same method as in Example 1 except that the coating speed and the coating amount of each composition were applied so as to be the thickness of the laminate and the thickness of each layer described in Table 1, respectively. Was used to obtain an adhesive sheet for printing.

Example 6
(1) Formation of coating film (z ′) and coating film (y ′) The composition (z) prepared in Production Example 4 using an applicator on the release agent layer of the release film (1) as a release material. ) And a coating film (y ′) composed of the composition (yb) prepared in Production Example 3 was sequentially formed on the coating film (z).
In addition, the coating speed and the 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 described in Table 1. did.
(2) Drying treatment of (z ′) and coating film (y ′) The formed coating film (z ′) and coating film (y ′) were simultaneously dried at a drying temperature of 110 ° C. for 120 seconds to give a release film (1 The layered product in which the layer (Z) and the layer (Y) were directly laminated was formed in this order from the release agent layer.
(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.
In addition, the coating speed and coating amount of the composition (x) for forming the coating film (x ′) were adjusted to be the thickness of the laminate and the thickness of each layer described 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 stuck on the surface of the exposed layer (Y) to form a laminated body to obtain an adhesive sheet for printing.

Comparative Example 1
On the release agent layer of the release film (1), which is a release material, a coating film (z ′) made of the composition (z) prepared in Production Example 4 is formed and dried at a drying temperature of 110 ° C. for 120 seconds to form a layer. (Z) was formed.
Further, on the release agent layer of the release film (2) prepared separately from the release film on the layer (Z), a coating film (x ′) composed of the composition (x) prepared in Production Example 1 is formed, Drying was performed at a drying temperature of 110 ° C. for 120 seconds to form a layer (X).
And a base film is laminated | stacked as a layer (Y) on the surface of the layer (X) which has exposed, and also a layer (Z) is crimped | bonded on a base film with a heating roll at 140 degreeC. A laminated body was formed by laminating, and a pressure-sensitive adhesive sheet for printing printing in which the laminated body was sandwiched between two release materials was obtained.

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

Comparative Example 3
The composition (yb) prepared in Production Example 3 was used in place of the composition (ya), and the coating film (z ′), coating film (y ′), and coating film (x ′) The method similar to that of Comparative Example 2 except that the coating speed and the coating amount of each composition for forming the film were adjusted to the thickness of the laminate and the thickness of each layer described in Table 1, respectively. Was used to obtain an adhesive sheet for printing.

The thicknesses of the laminates that the pressure-sensitive adhesive sheets for printing and printing produced in Examples and Comparative Examples have, and the thicknesses of the layers (X), (Y), and layers (Z) constituting the laminates are described above. Measured according to the method. Moreover, the thickness ratio of the layer (X) to the total thickness 100 of the layer (Y) and the layer (Z) was also calculated using the obtained results. The measurement results are shown in Table 1.

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

<Breaking strength, breaking elongation, yield strength, yield elongation, elastic modulus>
The pressure-sensitive adhesive sheet for printing and printing produced in Examples and Comparative Examples was cut into a size of 120 mm in length and 15 mm in width, and each release material on the pressure-sensitive adhesive layer (X) and the printing and printing layer (Z) was removed. This was used as a test sample.
In accordance with JIS 7161: 1994, using a universal material testing machine (product name “Tensilon RTG-1225” manufactured by A & D Co., Ltd.), the distance between chucks is 100 mm and the tensile speed is 200 mm / min. The rupture strength, rupture elongation, yield strength, yield elongation, and elastic modulus of the test sample in the MD direction were measured.
The “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.

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

<Curved surface followability>
The release film (1) on the print printing layer (Z) of the pressure-sensitive adhesive sheet for printing and printing produced in Examples and Comparative Examples was removed, and the pressure-sensitive adhesive sheet (product name “PET100” manufactured by Lintec Corporation) was used as the pressure-sensitive adhesive sheet for lining. A) PL thin ”) was bonded to the printed printing layer (Z) surface, and then cut into a size of 250 mm long × 22 mm wide.
Then, the release film (2) on the pressure-sensitive adhesive layer (X) is removed, and the surface of the exposed pressure-sensitive adhesive layer (X) is placed on a cylinder in 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 leaving still for 7 days in the environment of 23 degreeC and 50% RH (relative humidity), the amount of floating peeling from a to-be-adhered body was measured.

<Printability>
The printing / printing pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were subjected to bar code reading evaluation in accordance with JIS L0849 (2004) to evaluate printability.
In detail, first, using the thermal transfer printer (product name “140XiIII” manufactured by Zebra Technologies Co., Ltd.) and the thermal transfer ribbon (product name “TR4070” manufactured by Dexerials Co., Ltd.), prints produced in Examples and Comparative Examples were used. A barcode was printed on the adhesive sheet.
Then, using a bar code reading verification machine (RJS, product name “INSPECTOR 3000”), according to ANSI (American National Standards Institute) X3.182 (1990) standard Bar Code Quality Guideline, 5 grades (Excellent A> B >C>D> F inferior) was evaluated for barcode reading.

<Tamper resistance>
The pressure-sensitive adhesive sheet for printing and printing produced in the examples and comparative examples was cut into a size of 300 mm long × 25 mm wide to produce an evaluation sample. The release film (1) on the printed printing layer (Z) of the evaluation sample was removed, and printing was performed on the printed printing layer (Z) in accordance with the evaluation method for printability.
Then, the release film (2) on the pressure-sensitive adhesive layer (X) is removed, and the surface of the pressure-sensitive adhesive layer (X) is exposed to a stainless steel plate (23 ° C., 50% RH (relative humidity) environment). SUS304, No. 360) was affixed and allowed to stand for 24 hours in the same environment.
After leaving still for 24 hours, it was peeled off from the stainless steel plate at a pulling speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000.
Thereafter, it was affixed to the stainless steel plate again, bar code readability was evaluated according to the above-described printability evaluation method, and the falsification prevention property of the adhesive sheet for printing and printing was evaluated according to the following criteria.
A: The printed surface was deformed, and the barcode readability (five-step evaluation) deteriorated before and after peeling. (Excellent tamper resistance).
F: The printed surface was not deformed, and the barcode readability (five-level evaluation) did not change before and after peeling. (Inferior to tampering prevention).

<Interfacial adhesion>
The pressure-sensitive adhesive sheet for printing and printing produced in Examples and Comparative Examples was cut into a size of 50 mm long × 30 mm wide. And it evaluated based on JISK5600-5-6.
The interfacial adhesion between the base material layer (Y) and the print printing layer (Z) was evaluated according to the following criteria.
A: The classification according to JIS K5600-5-6 was “0 (best)”.
B: The classification according to JIS K5600-5-6 was “1” to “4”.
F: The classification according to JIS K5600-5-6 was “5 (worst)”.

As shown in Table 2, the adhesive sheets for printing and printing of Examples 1 to 6 are different from the adhesive sheets for printing and printing of Comparative Examples 1 to 3 with the base material layer (Y) and the printing and printing layer (Z). Due to high interfacial adhesion, peeling at the interface between the base material layer (Y) and the printing layer (Z) hardly occurs even when affixing to a curved surface, and it is excellent in punching processability and cutting processability. It is considered a thing.
In addition, the adhesive sheets for printing and printing of Comparative Examples 1 to 3 have low interfacial adhesion between the substrate layer (Y) and the printing and printing layer (Z). There is a possibility that peeling at the interface with the printing layer (Z) may occur, and there is a possibility that the punching processability and the cutting processability may be adversely affected.
Furthermore, the pressure-sensitive adhesive sheet for printing of Comparative Example 1 was inferior in both tamper resistance and curved surface followability.

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, for coating masking, for surface protection of a metal plate, etc., and used in a place where curved surface followability is required. .

1, 2 Printing / printing adhesive sheet 10 Laminate 11 Base material layer (Y)
12 Adhesive layer (X)
13 Printing layer (Z)
141 Release material

Claims

A pressure-sensitive adhesive sheet for printing printing having a laminate in which a pressure-sensitive adhesive layer (X), a base material layer (Y), and a printing printing layer (Z) are laminated in this order,
The laminate is
A coating film (z ′) comprising a composition (z) containing a non-adhesive resin (z1) which is a forming material of the printing layer (Z);
A coating film (y ′) comprising a composition (y) containing at least one non-adhesive resin (y1) selected from the group consisting of an acrylic urethane-based resin and an olefin-based resin that is a forming material of the base material layer (Y) )When,
Are laminated in this order, and at least the coating films (z ′) and (y ′) are simultaneously dried to form a laminate,
In the laminate, the pressure-sensitive adhesive sheet for printing and printing, wherein the pressure-sensitive adhesive layer (X) is a layer formed from a composition (x) containing a pressure-sensitive resin that is a material for forming the pressure-sensitive adhesive layer (X).
The laminate is
After directly laminating the coating film (z ′), the coating film (y ′), and the coating film (x ′) made of the composition (x) in this order, the coating film (z ′) and the coating film (y The pressure-sensitive adhesive sheet for 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 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 being directly laminated in this order. Sheet.
The thickness ratio of the pressure-sensitive adhesive layer (X) to the total thickness 100 of the base material layer (Y) and the printing / printing layer (Z) is 20 to 110, according to any one of claims 1 to 3. Adhesive sheet for printing and printing.
The pressure-sensitive adhesive sheet for printing according to any one of claims 1 to 4, wherein the thickness of the laminate is 2 to 90 µm.
The pressure-sensitive adhesive sheet for 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 pressure-sensitive adhesive sheet for 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 according to any one of claims 1 to 7, wherein the non-adhesive resin (y1) is an ultraviolet non-curable resin having no polymerizable functional group.
The pressure-sensitive adhesive sheet for printing according to any one of claims 1 to 8, wherein the base material layer (Y) is an unstretched sheet-like material.
The pressure-sensitive adhesive sheet for 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 pressure-sensitive adhesive sheet for printing according to any one of claims 1 to 10, wherein the elongation at break is 100% or more.
The pressure-sensitive adhesive sheet for printing according to any one of claims 1 to 11, having a breaking strength of 32 MPa or less.
The pressure-sensitive adhesive sheet for printing according to any one of claims 1 to 12, which has an elastic modulus of 500 MPa or less.
A method for producing an adhesive sheet for printing and printing according to any one of claims 1 to 13,
The manufacturing method of the adhesive sheet for printing printing which has the following process (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.
-Process (2A): The process of drying a coating film (z ') and a coating film (y') simultaneously, and forming a printing printing layer (Z) and a base material layer (Y).
The manufacturing method of the adhesive sheet for printing of Claim 14 which has the following process (1B) and (2B).
Step (1B): a coating film (z ′) comprising the composition (z), a coating film (y ′) comprising the composition (y), and a coating film (x ′) comprising the composition (x) A process of directly stacking layers in this order.
-Process (2B): The process of drying a coating film (z '), a coating film (y'), and a coating film (x ') simultaneously, and forming the said laminated body.
The manufacturing method of the adhesive sheet for printing printing of Claim 15 which apply | coats a composition (z), a composition (y), and a composition (x) simultaneously in a process (1B).
The method for producing a pressure-sensitive adhesive sheet for printing according to any one of claims 14 to 16, wherein the composition (z) and the composition (y) each independently further contain a diluting solvent.