JP2020111622A - Adhesive laminated film and structure - Google Patents

Abstract

To provide an adhesive laminated film which can suppress adhesive residue on an ITO film when being heated in a state of being stuck to the ITO film.SOLUTION: An adhesive laminated film 50 for protecting a surface of an indium tin oxide (ITO) film includes a base material layer 10 and an adhesive resin layer 20 provided on one surface of the base material layer 10, in which the adhesive resin layer 20 includes a structural unit derived from (meth)acrylonitrile.SELECTED DRAWING: Figure 1

Description

The present invention relates to an adhesive laminated film and a structure.

A transparent conductive film on which an indium tin oxide (ITO) film is formed is used for a touch panel, electronic paper, and the like. A surface protective film may be attached to the transparent conductive film in order to prevent the surface from being soiled or damaged.

Examples of the technique relating to the surface protection film used for such a transparent conductive film include those described in Patent Document 1 (JP-A-2015-202681).

Patent Document 1 discloses a surface protective film for protecting the surface of the transparent conductive film opposite to the surface on which the transparent conductive film is formed, which has a coating layer on at least one surface of the laminated polyester film, A surface protective film for a conductive film is described, in which the amount of ester cyclic trimer deposited on the surface of the coating layer is 1.2 mg/m ² or less when heated at 150° C. for 90 minutes.

JP, 2005-202681, A

According to the studies by the present inventors, the following problems have been found regarding the surface protective film used for the transparent conductive film having the ITO film formed thereon.
First, in order to perform the crystallization treatment of the ITO film, the heat treatment may be performed with the surface protection film attached to the ITO film side of the transparent conductive film.
The present inventors have found that when heat treatment is performed with the surface protection film attached to the ITO film, a glue residue phenomenon occurs in which a part of the adhesive resin layer remains on the ITO film after the heat treatment. It was discovered that there are cases where it will end.

The present invention has been made in view of the above circumstances, and provides an adhesive laminated film capable of suppressing adhesive residue on an ITO film when heat treatment is performed in a state of being attached to the ITO film. Is.

The present inventors have earnestly studied to achieve the above object. As a result, by using an adhesive resin layer containing a constitutional unit derived from (meth)acrylonitrile as the adhesive resin layer constituting the adhesive laminated film, when heat treatment was performed in a state of being attached to the ITO film. The present invention has been completed by finding that it is possible to suppress the adhesive residue on the ITO film.

According to the present invention, the following adhesive laminated film and structure are provided.

[1]
An adhesive laminated film for protecting the surface of an indium tin oxide (ITO) film, comprising:
A base material layer and an adhesive resin layer provided on one surface of the base material layer,
An adhesive laminated film in which the adhesive resin layer contains a structural unit derived from (meth)acrylonitrile.
[2]
In the adhesive laminated film according to the above [1],
The content of the structural unit derived from the (meth)acrylonitrile in the adhesive resin layer is 10% by mass or more and 30% by mass or less when the whole of the adhesive resin layer is 100% by mass. ..
[3]
In the adhesive laminated film according to the above [1] or [2],
The adhesive resin layer contains a (meth)acrylic adhesive resin, and the (meth)acrylic adhesive resin contains a structural unit derived from the (meth)acrylonitrile.
[4]
In the adhesive laminated film according to any one of [1] to [3] above,
Peel strength (P ₀ ) between the ITO film vapor-deposited on the substrate film and the adhesive resin layer, measured by the following method, is 0.01 N/25 mm or more and 1.0 N/25 mm or less. Laminated film.
(Peeling strength measurement method)
The adhesive laminated film is attached to the ITO film so that the adhesive resin layer contacts the ITO film deposited on the substrate film. Then, using a tensile tester, the adhesive laminated film was peeled from the ITO film in the 180° direction at a temperature of 23° C. and a tensile speed of 300 mm/min, and the strength (N/25 mm) at that time was peeled. And
[5]
In the adhesive laminated film according to any one of [1] to [4] above,
When the adhesive laminate film is attached to the ITO film so that the adhesive resin layer is in contact with the ITO film deposited on the substrate film, and then the obtained structure is subjected to heat treatment at 150° C. for 60 minutes ,
The peel strength (P ₁ ) between the ITO film vapor-deposited on the substrate film and the adhesive resin layer, measured by the following method, is 0.1 N/25 mm or more and 1.0 N/25 mm or less. Adhesive laminated film.
(Peeling strength measurement method)
Using a tensile tester, the adhesive laminated film was peeled from the ITO film in the direction of 180 degrees under the conditions of 23° C. and a pulling speed of 300 mm/min, and the strength at that time (N/25 mm) was taken as the peel strength. ..
[6]
In the adhesive laminated film according to any one of [1] to [5] above,
An adhesive laminate film in which the adhesive resin layer has a thickness of 1 μm or more and 50 μm or less.
[7]
In the adhesive laminated film according to any one of the above [1] to [6],
The resin constituting the base material layer is polyolefin, polyester, polyamide, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyetherimide, ethylene/vinyl acetate copolymer, polyacrylonitrile, polycarbonate, polystyrene. , An adhesive laminated film containing one or more selected from ionomers, polysulfones, polyether sulfones and polyphenylene ethers.
[8]
An indium tin oxide (ITO) film,
A surface protective film attached to the ITO film,
A structure in which the surface protective film is the adhesive laminated film according to any one of [1] to [7].

ADVANTAGE OF THE INVENTION According to this invention, the adhesive laminated film which can suppress the adhesive residue on an ITO film at the time of heat-processing in the state stuck on the ITO film can be provided.

It is sectional drawing which showed typically an example of the structure of the adhesive laminated film of embodiment which concerns on this invention. It is sectional drawing which showed typically an example of the structure of the structure of embodiment which concerns on this invention.

Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description thereof will be omitted as appropriate. Moreover, the figure is a schematic view and does not match the actual dimensional ratio. Unless otherwise specified, “A to B” in the numerical range represents A or more and B or less. Further, in the present embodiment, “(meth)acrylic” means acrylic, methacrylic, or both acrylic and methacrylic.

1. Adhesive Laminated Film Hereinafter, the adhesive laminated film 50 according to the present embodiment will be described.
FIG. 1 is a cross-sectional view schematically showing an example of the structure of an adhesive laminated film 50 according to an embodiment of the present invention.

As shown in FIG. 1, an adhesive laminated film 50 according to the present embodiment is an adhesive laminated film for protecting the surface of an indium tin oxide (ITO) film, and includes a base material layer 10 and a base material layer. And an adhesive resin layer 20 provided on one surface of the adhesive layer 10. And in the adhesive laminated film 50 which concerns on this embodiment, the adhesive resin layer 20 contains the structural unit derived from (meth)acrylonitrile.

According to the study of the present inventors, when heat treatment is performed in a state where the surface protection film is attached to the ITO film, the adhesive residue that a part of the adhesive resin layer remains on the ITO film after the heat treatment. We have found that a phenomenon may occur.
Then, the inventors of the present invention have made extensive studies in order to achieve the above object. As a result, by using an adhesive resin layer containing a constitutional unit derived from (meth)acrylonitrile as an adhesive resin layer that constitutes the adhesive laminated film, when heat treatment was performed in a state of being attached to the ITO film. It was found for the first time that it is possible to suppress the adhesive residue on the ITO film.
That is, the pressure-sensitive adhesive laminated film 50 according to the present embodiment includes the pressure-sensitive adhesive resin layer 20 including the structural unit derived from (meth)acrylonitrile, so that the ITO film when heat-treated while being attached to the ITO film is obtained. It is possible to suppress the adhesive residue on the top.

In the pressure-sensitive adhesive laminated film 50 according to the present embodiment, the content of the structural unit derived from (meth)acrylonitrile in the pressure-sensitive adhesive resin layer 20 is on the ITO film when heat treatment is performed in a state of being attached to the ITO film. From the viewpoint of further suppressing the adhesive residue of 10% by mass, when the entire adhesive resin layer 20 is 100% by mass, it is preferably 10% by mass or more, more preferably 12% by mass or more, and 15% by mass. The above is particularly preferable.
In addition, in the pressure-sensitive adhesive laminated film 50 according to the present embodiment, the content of the structural unit derived from (meth)acrylonitrile in the pressure-sensitive adhesive resin layer 20 depends on the adhesive force to the ITO film before the heat treatment, that is, the initial adhesive force. From the viewpoint of making it even better, when the entire adhesive resin layer 20 is 100% by mass, it is preferably 30% by mass or less, more preferably 28% by mass or less, and 25% by mass or less. It is more preferable that the content is 23% by mass or less, and particularly preferably 23% by mass or less.

In the present embodiment, for example, the content ratio of the structural unit derived from (meth)acrylonitrile in the pressure-sensitive adhesive resin (P) forming the pressure-sensitive adhesive resin layer 20 and the content ratio of the pressure-sensitive adhesive resin (P) in the pressure-sensitive adhesive resin layer 20. It is possible to control the content of the structural unit derived from (meth)acrylonitrile in the adhesive resin layer 20 within the above range by appropriately adjusting the above.

In the pressure-sensitive adhesive laminated film 50 according to this embodiment, from the viewpoint of further improving the initial pressure-sensitive adhesive force and suppressing the pressure-sensitive adhesive laminated film 50 from rising from the ITO film, The peel strength (P ₀ ) between the ITO film deposited on the material film and the adhesive resin layer 20 is preferably 0.01 N/25 mm or more, more preferably 0.02 N/25 mm or more, More preferably, it is 0.03 N/25 mm or more.
Further, in the adhesive laminated film 50 according to the present embodiment, it is measured by the following method from the viewpoint of further suppressing the adhesive residue on the ITO film when the heat treatment is performed in the state of being attached to the ITO film. The peel strength (P ₀ ) between the ITO film deposited on the substrate film and the adhesive resin layer 20 is preferably 1.0 N/25 mm or less, and more preferably 0.5 N/25 mm or less. It is more preferably 0.2 N/25 mm or less.
(Peeling strength measurement method)
The adhesive laminated film 50 is attached to the ITO film so that the adhesive resin layer 20 is in contact with the ITO film deposited on the base film. Then, using a tensile tester, the adhesive laminate film 50 was peeled from the ITO film in the direction of 180 degrees at 23° C. and a pulling speed of 300 mm/min, and the strength (N/25 mm) at that time was taken as the peel strength. To do.

In the pressure-sensitive adhesive laminated film 50 according to the present embodiment, the pressure-sensitive adhesive laminated film is attached to the ITO film so that the pressure-sensitive adhesive resin layer 20 is in contact with the ITO film vapor-deposited on the substrate film, and then the obtained structure is formed. When heat-treated at 150° C. for 60 minutes, the peel strength (P ₁ ) between the ITO film vapor-deposited on the substrate film and the adhesive resin layer 20 measured by the following method is 0.1 N/25 mm or more. It is preferably 1.0 N/25 mm or less. This further suppresses the adhesive residue on the ITO film when the heat treatment is performed in the state of being attached to the ITO film, and prevents the adhesive laminated film 50 from rising from the ITO film after the heat treatment. It can be further suppressed.
(Peeling strength measurement method)
Using the tensile tester, the adhesive laminated film 50 is peeled from the ITO film in the 180 degree direction under the conditions of 23° C. and a pulling speed of 300 mm/min, and the strength (N/25 mm) at that time is taken as the peel strength.

The total thickness of the pressure-sensitive adhesive laminated film 50 according to the present embodiment is preferably 2 μm or more and 550 μm or less, more preferably 6 μm or more and 330 μm or less, and further preferably 12 μm or more and 165 μm from the viewpoint of the balance between mechanical properties and handleability. It is as follows.

Next, each layer which comprises the adhesive laminated film 50 which concerns on this embodiment is demonstrated.

<Base material layer>
The base material layer 10 is a layer provided for the purpose of further improving the handleability, mechanical properties, heat resistance and other properties of the adhesive laminated film 50.
The base material layer 10 is not particularly limited, and examples thereof include a resin film.

Examples of the resin forming the base material layer 10 include polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene), and poly(1-butene); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. Polyester; nylon-6, nylon-66, polyamides such as polymethaxylene adipamide; polyacrylate; polymethacrylate; polyvinyl chloride; polyvinylidene chloride; polyimide; polyetherimide; ethylene vinyl acetate copolymer; poly Acrylonitrile; Polycarbonate; Polystyrene; Ionomer; Polysulfone; Polyethersulfone; Polyphenylene ether, and the like.
Among these, one or more selected from polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyimide are preferable from the viewpoint of excellent balance of heat resistance and transparency, mechanical strength, price, etc., and polypropylene and polyethylene are preferable. At least one selected from terephthalate and polyethylene naphthalate is more preferable.

The base material layer 10 may be a single layer or two or more types of layers.
The form of the resin film used to form the base material layer 10 may be a stretched film or a film uniaxially or biaxially stretched. From the viewpoint of improving heat resistance and mechanical strength, the film is preferably a uniaxially or biaxially stretched film.

The thickness of the base material layer 10 is preferably 1 μm or more and 500 μm or less, more preferably 5 μm or more and 300 μm or less, and further preferably 10 μm or more and 150 μm or less from the viewpoint of obtaining good film characteristics.
The base material layer 10 may be surface-treated in order to improve the adhesiveness with other layers. Specifically, corona treatment, plasma treatment, undercoat treatment, primer coat treatment, or the like may be performed.

<Adhesive resin layer>
The adhesive resin layer 20 is a layer that is provided on one surface side of the base material layer 10 and is in contact with the surface of the ITO film to adhere thereto, and is a layer for attaching the adhesive laminated film 50 to the ITO film. is there.

The adhesive resin layer 20 contains a structural unit derived from (meth)acrylonitrile, for example, an adhesive resin (P) containing a structural unit derived from (meth)acrylonitrile.
Examples of the adhesive resin (P) containing a structural unit derived from (meth)acrylonitrile include (meth)acrylic adhesive resin, silicone adhesive resin, urethane adhesive resin, olefin adhesive resin, and styrene adhesive. Examples thereof include adhesive resins.
Among these, the (meth)acrylic adhesive resin is preferable from the viewpoint of facilitating the adjustment of the content of the structural unit derived from (meth)acrylonitrile.

Examples of the (meth)acrylic adhesive resin used in the adhesive resin layer 20 include a structural unit (A) derived from (meth)acrylic acid alkyl ester and a structural unit (B) derived from (meth)acrylonitrile. A copolymer is mentioned.
In the present embodiment, the (meth)acrylic acid alkyl ester means an acrylic acid alkyl ester, a methacrylic acid alkyl ester, or a mixture thereof.

The (meth)acrylic adhesive resin according to the present embodiment includes, for example, a (meth)acrylic acid alkyl ester monomer, a (meth)acrylonitrile monomer, and if necessary, a (meth)acrylic acid alkyl ester monomer and (meth) It can be obtained by copolymerizing a mixture containing an acrylonitrile monomer and another monomer copolymerizable with the acrylonitrile monomer.

Examples of the (meth)acrylic acid alkyl ester monomer forming the structural unit (A) derived from the (meth)acrylic acid alkyl ester include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , Isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, (meth) Hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, (meth ) Decyl acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (meth) Hexadecyl acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl acrylate, and the like (meth)acrylate alkyl having a carbon number of 1 to 20 Examples thereof include esters. These may be used alone or in combination of two or more.
Among these, (meth)acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferable, and (meth)acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is more preferable. ..
Specific examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. These may be used alone or in combination of two or more.
In the (meth)acrylic pressure-sensitive adhesive resin according to the present embodiment, the content of the structural unit (A) derived from the (meth)acrylic acid alkyl ester is the total of all structural units in the (meth)acrylic pressure-sensitive adhesive resin. When it is 100 mass %, it is preferably 50 mass% or more and 95 mass% or less, and more preferably 55 mass% or more and 92 mass% or less.

Examples of the (meth)acrylonitrile monomer forming the structural unit (B) derived from (meth)acrylonitrile include acrylonitrile, methacrylonitrile, and a mixture thereof.
In the (meth)acrylic adhesive resin according to the present embodiment, the content of the structural unit (B) derived from (meth)acrylonitrile is 100% by mass based on the total amount of all the structural units in the (meth)acrylic adhesive resin. Is preferably 10% by mass or more and 30% by mass or less, more preferably 12% by mass or more and 28% by mass or less, further preferably 15% by mass or more and 25% by mass or less, and 15% by mass. % To 23% by mass is particularly preferable.

The (meth)acrylic adhesive resin according to the present embodiment can be copolymerized with a (meth)acrylic acid alkyl ester monomer and a (meth)acrylonitrile monomer from the viewpoint of improving cohesive force, heat resistance, cross-linking property, and the like. It may further include a structural unit (C) derived from another monomer.
Examples of the monomer forming the structural unit (C) include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and other carboxyl group-containing monomers; maleic anhydride; Acid anhydride group-containing monomers such as itaconic anhydride; hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxy (meth)acrylate Hexyl, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, hydroxyl group-containing monomers such as (4-hydroxymethylcyclohexyl)methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, Sulfonic acid group-containing monomer such as 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl(meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid; 2-hydroxyethylacryloyl Phosphate group-containing monomers such as phosphate; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, (N-Substituted)amide-based monomers such as N-methylol (meth)acrylamide and N-methylolpropane (meth)acrylamide; aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth ) Aminoalkyl (meth)acrylate monomers such as t-butylaminoethyl acrylate; alkoxyalkyl (meth)acrylate monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; N-cyclohexyl Maleimide monomers such as maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide; N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2- Itaconimide-based monomers such as ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl Succinimide-based monomers such as 6-oxyhexamethylenesuccinimide and N-(meth)acryloyl-8-oxyoctamethylenesuccinimide; vinyl esters such as vinyl acetate and vinyl propionate; N-vinyl-2-pyrrolidone and N-methyl Vinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2 -Nitrogen-containing heterocyclic monomers such as pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine; N-vinylcarboxylic acid amides; styrenes such as styrene and α-methylstyrene Monomers; lactam monomers such as N-vinylcaprolactam; epoxy group-containing acrylic monomers such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene (meth)acrylate. Glycols, glycol-based acrylic ester monomers such as methoxy polypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, heterocycles such as silicone (meth)acrylate, halogen atoms, silicon atoms, etc. Acrylic ester-based monomer having; hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di( (Meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinylbenzene, butyl di(meth)acrylate, hexyl di( Examples thereof include polyfunctional monomers such as (meth)acrylate; olefinic monomers such as isoprene, butadiene and isobutylene; vinyl ether type monomers such as methyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more.
Among these, one or more selected from carboxyl group-containing monomers, hydroxyl group-containing monomers, (N-substituted)amide-based monomers, epoxy group-containing acrylic monomers and polyfunctional monomers are preferable, and acrylic acid and methacrylic acid are preferable. , Itaconic acid, maleic acid, fumaric acid, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, (meth)acrylamide, N-methylol One or more selected from (meth)acrylamide, glycidyl (meth)acrylate and divinylbenzene are more preferable.
In the (meth)acrylic adhesive resin according to the present embodiment, the content of the structural unit (C) is 0 mass when the total of all structural units in the (meth)acrylic adhesive resin is 100% by mass. % Or more and 40% by mass or less, preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.

In the adhesive resin layer 20 according to the present embodiment, while having a better initial adhesive force, it is possible to further suppress the adhesive residue on the ITO film when the heat treatment is performed in the state of being attached to the ITO film. From the viewpoint, the adhesive resin (P) containing the structural unit derived from (meth)acrylonitrile is preferably used in combination with two or more kinds of resins having different contents of the structural unit derived from (meth)acrylonitrile.
More specifically, the structural unit derived from (meth)acrylonitrile is preferably 15% by mass or more and 30% by mass or less, and more preferably 17% by mass based on 100% by mass of all the structural units in the adhesive resin (P). % To 28% by mass of the adhesive resin (P1) and 100% by mass of all the constituent units in the adhesive resin (P), the (meth)acrylonitrile-derived structural unit is preferably 3% by mass or more and 15% by mass or more. It is more preferable to use in combination with an adhesive resin (P2) containing less than 5% by mass, more preferably 5% by mass or more and 13% by mass or less.
By including the adhesive resin (P1), it is possible to further suppress the adhesive residue on the ITO film when the heat treatment is performed in the state of being attached to the ITO film. Further, by containing the adhesive resin (P2), the initial adhesive strength can be further improved.

When the adhesive resin layer 20 includes the adhesive resin (P1) and the adhesive resin (P2) having different content of the structural unit derived from (meth)acrylonitrile, the adhesive resin (P1) contained in the adhesive resin layer 20 ( The content of P1) is on the ITO film when heat treatment is performed in a state of being attached to the ITO film, when the total content of the adhesive resin (P1) and the adhesive resin (P2) is 100% by mass. From the viewpoint of further suppressing the adhesive residue, it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, and 70% by mass or more. Is even more preferable, and particularly preferably 75% by mass or more.
Further, from the viewpoint of further suppressing the adhesive residue on the ITO film when the adhesive laminated film 50 is attached to the ITO film and stored under high temperature and high humidity, heat treatment is performed, The content of the adhesive resin (P1) contained in the resin layer 20 is preferably 80% by mass or more, and more preferably 85% by mass or more.

Moreover, when the adhesive resin layer 20 contains the adhesive resin (P1) and the adhesive resin (P2) in which the content of the structural unit derived from (meth)acrylonitrile is different, the adhesive resin (P1) contained in the adhesive resin layer 20 ( The content of P1) is 97% by mass or less from the viewpoint of obtaining a better initial adhesive strength when the total content of the adhesive resin (P1) and the adhesive resin (P2) is 100% by mass. It is preferably present, more preferably 95% by mass or less, further preferably 93% by mass or less.

Here, the content of (meth)acrylonitrile in the adhesive resin layer 20 can be quantified by, for example, ¹ H-NMR and ¹³ C-NMR analysis.

For the production of the (meth)acrylic pressure-sensitive adhesive resin according to the present embodiment, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization and various radical polymerization can be appropriately selected. In solution polymerization in radical polymerization, ethyl acetate, toluene, etc. are used as a polymerization solvent.

The polymerization initiator, chain transfer agent, emulsifier and the like used in the radical polymerization are not particularly limited and can be appropriately selected and used.
The polymerization initiator is not particularly limited, but, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis[2-(5 -Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine) , 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd., VA-057) and other azo initiators; sodium persulfate, Persulfates such as potassium persulfate and ammonium persulfate; di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butyl Peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di(4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, t-butylhydroper Peroxide initiators such as oxides and hydrogen peroxide; Combination of persulfates and sodium bisulfite; Redox initiators such as combinations of peroxides and sodium ascorbate and peroxides and reducing agents Can be mentioned.
The above polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is preferably 0.005 to 1 part by mass and more preferably 0.02 to 0.6 part by mass with respect to 100 parts by mass of the monomer.

A chain transfer agent may be used in the polymerization. By using a chain transfer agent, the molecular weight of the (meth)acrylic adhesive resin can be adjusted appropriately.
Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent used is, for example, 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the monomer.

Examples of the emulsifier used in the case of emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and the like. Anionic emulsifiers; nonionic emulsifiers such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene block polymers, and the like. These emulsifiers may be used alone or in combination of two or more.

The content of the adhesive resin (P) containing the structural unit derived from (meth)acrylonitrile in the adhesive resin layer 20 according to the present embodiment is from the viewpoint of the balance between the initial adhesive force and the suppression of adhesive residue. When the total amount of the organic resin layer 20 is 100% by mass, it is preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 99% by mass or less, and 80% by mass or more and 98% by mass. The amount is more preferably the following or less, and particularly preferably 85% by mass or more and 97% by mass or less.

From the viewpoint of adjusting the adhesive force and cohesive force of the adhesive resin (P), the adhesive resin layer 20 according to the present embodiment, in addition to the adhesive resin (P) containing a structural unit derived from (meth)acrylonitrile, It is preferable to further include a cross-linking agent having two or more cross-linkable functional groups in one molecule.
Examples of such a cross-linking agent include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl ether and the like. Epoxy compounds; Tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylol propane toluene diisocyanate 3 adduct, polyisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and other isocyanate compounds; trimethylol propane-tri-β-aziridinyl propio , Tetramethylolmethane-tri-β-aziridinylpropionate, N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), N,N′-hexamethylene-1,6- Aziridine compounds such as bis(1-aziridinecarboxamide), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-(2-methylaziridine)propionate; Tetrafunctional epoxy compounds such as N,N,N′,N′-tetraglycidyl-m-xylenediamine and 1,3-bis(N,N′-diglycidylaminomethyl)cyclohexane; hexamethoxymethylolmelamine and the like A melamine compound etc. are mentioned. These cross-linking agents may be used alone or in combination of two or more.
Among these, it is preferable to contain one kind or two or more kinds selected from an epoxy compound, an isocyanate compound and an aziridine compound, and an epoxy compound is more preferable.

The content of the cross-linking agent in the adhesive resin layer 20 according to the present embodiment is based on 100 parts by mass of the adhesive resin (P) from the viewpoint of improving the balance between the initial adhesive force and the suppression of adhesive residue. The amount is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less, still more preferably 1 part by mass or more and 6 parts by mass or less.

From the viewpoint of adjusting the adhesive force and cohesive force of the adhesive resin (P), the adhesive resin layer 20 further contains a surfactant in addition to the adhesive resin (P) containing a structural unit derived from (meth)acrylonitrile. It is preferable to include.
Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.

Examples of the cationic surfactant include dodecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didodecyldimethylammonium chloride and ditetradecyldimethylammonium chloride. Chloride, dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, dodecylbenzyldimethylammonium chloride, hexadecylbenzyldimethylammonium chloride, octadecylbenzyldimethylammonium chloride, palmityltrimethylammonium chloride, oleyltrimethylammonium chloride, divalmitylbenzylmethyl chloride Ammonium chloride, dioleoyl benzyl methyl ammonium chloride, etc. are mentioned.

Examples of the anionic surfactant include alkyl diphenyl ether disulfonates such as diammonium dodecyl diphenyl ether disulfonate, sodium dodecyl diphenyl ether disulfonate, calcium dodecyl diphenyl ether disulfonate, sodium alkyl diphenyl ether disulfonate; sodium dodecyl benzene sulfonate, dodecyl benzene. Alkylbenzene sulfonates such as ammonium sulfonate; Alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate; Aliphatic carboxylates such as sodium fatty acid and potassium oleate; Sulfate salts containing polyoxyalkylene units (for example, polyoxy Polyoxyethylene alkyl ether sulfates such as sodium ethylene alkyl ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; Polyoxyethylene alkylphenyl ether sulfates such as sodium polyoxyethylene alkylphenyl ether sulfate and ammonium polyoxyethylene alkylphenyl ether sulfate Polyoxyethylene polycyclic phenyl ether sodium sulfate, polyoxyethylene polycyclic phenyl ether ammonium sulfate and other polyoxyethylene polycyclic phenyl ether sulfate ester salts, etc.); naphthalene sulfonic acid formalin condensate sodium and other naphthalene sulfonic acid formalin condensate salts; Alkyl sulfosuccinates such as sodium dialkyl sulfosuccinate, disodium monoalkyl sulfosuccinate; polyoxyethylene-polyoxypropylene glycol ether sulfate; sulfonate or sulfate ester group and polymerizable carbon-carbon (unsaturated) di Examples thereof include a surfactant having a heavy bond in the molecule.

As the nonionic surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene alkyl ether compounds such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, Polyoxyalkylene alkylphenyl ether compounds such as polyoxyethylene nonylphenyl ether, polyoxyalkylene unit-containing ether compounds such as polyoxyalkylene polycyclic phenyl ether compounds such as polyoxyethylene polycyclic phenyl ether; polyoxyethylene monolaurate, Polyoxyalkylene alkyl ester compounds such as polyoxyethylene monostearate and polyoxyethylene monooleate; polyoxyalkylene alkylamine compounds such as polyoxyethylene alkylamine; sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, Examples thereof include sorbitan compounds such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monooleate.

Examples of the amphoteric surfactant include lauryl betaine and lauryl dimethylamine oxide.

These surfactants may be used alone or in combination of two or more.
Among these, nonionic surfactants are preferable, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene alkyl ether compounds such as polyoxyethylene oleyl ether are more preferable, and polyoxyethylene Alkyl ether compounds are more preferred.

The content of the surfactant in the adhesive resin layer 20 according to the present embodiment is 100 parts by mass of the adhesive resin (P) from the viewpoint of improving the balance between the initial adhesive force and the suppression of adhesive residue. 0.1 to 15 parts by mass is preferable, 0.5 to 10 parts by mass is more preferable, and 1 to 8 parts by mass is further preferable.

The adhesive resin layer 20 includes a tackifier, a plasticizer, an antioxidant, an antioxidant, a colorant (a pigment or a dye, etc.), a softener, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, if necessary. Other components such as an inorganic or organic filler, metal powder, particulate matter, foil-like matter and the like may be further blended.

The thickness of the adhesive resin layer 20 is not particularly limited, but is preferably 1 μm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less from the viewpoint of the balance between the initial adhesive force and the suppression of adhesive residue. It is more preferably 2 μm or more and 15 μm or less, and particularly preferably 3 μm or more and 12 μm or less.

<Other layers>
In the adhesive laminated film 50 according to the present embodiment, a release film may be further laminated on the adhesive resin layer 20. Examples of the release film include a polyester film that has been subjected to a release treatment.

<Method for producing adhesive laminated film>
Next, an example of a method for manufacturing the adhesive laminated film 50 according to the present embodiment will be described.
The adhesive laminated film 50 according to the present embodiment can be obtained, for example, by forming the adhesive resin layer 20 on one surface of the base material layer 10.

The adhesive resin layer 20 is formed by, for example, applying an adhesive resin (P), and optionally an adhesive containing a crosslinking agent, a surfactant, other components, etc., onto the base material layer 10. You can The pressure-sensitive adhesive may be used as a coating liquid by dissolving the pressure-sensitive adhesive resin (P), if necessary, a crosslinking agent, a surfactant, and other components in an organic solvent, or may be emulsified in water to form an aqueous emulsion. May be used as. Further, when the adhesive is liquid, it may be used as it is.
As a method for applying the pressure-sensitive adhesive on the base material layer 10, a conventionally known coating method, for example, a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, a die coater method or the like is adopted. it can. The drying conditions of the applied pressure-sensitive adhesive are not particularly limited, but it is generally preferable to dry the pressure-sensitive adhesive in the temperature range of 80 to 200° C. for 10 seconds to 10 minutes. More preferably, it is dried at 80 to 170° C. for 15 seconds to 5 minutes. In order to sufficiently accelerate the crosslinking reaction between the crosslinking agent and the adhesive resin, the adhesive may be heated at 40 to 80° C. for about 5 to 300 hours after completion of drying.
The base material layer 10 and the adhesive resin layer 20 may be formed by coextrusion molding, or may be formed by laminating the film-shaped base material layer 10 and the film-shaped adhesive resin layer 20. You may.

When the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive resin layer 20 is an aqueous emulsion, it is preferable to include, for example, an organic solvent in order to improve the coatability of the pressure-sensitive adhesive to the base material layer 10. Examples of the organic solvent include lower aliphatic alcohols such as methanol, ethanol, isopropanol (IPA), n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate; Examples thereof include diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; hydrophilic organic solvents such as diacetone alcohol. Among these, diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether are preferable.
These organic solvents may be used alone or in combination of two or more.
Further, one or more of toluene, xylene, hexane, ethyl heptane acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used in combination with these hydrophilic organic solvents. ..
The amount of the organic solvent used is 0.1 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the adhesive resin (P) from the viewpoint of improving the balance between the initial adhesive strength and the suppression of adhesive residue. Is more preferable, 0.5 parts by mass or more and 10 parts by mass or less is more preferable, and 1 part by mass or more and 8 parts by mass or less is further preferable.

2. Structure Next, the structure 100 according to the present embodiment will be described. FIG. 2 is a cross-sectional view schematically showing an example of the structure of the structure 100 according to the embodiment of the present invention.

As shown in FIG. 2, the structure 100 according to the present embodiment includes an indium tin oxide (ITO) film 70 and a surface protective film attached to the ITO film 70, and the surface protective film is the present embodiment. It is an adhesive laminated film 50 according to. The ITO film 70 is formed on the base material layer 90, for example.
Since the structure 100 according to the present embodiment includes the adhesive laminated film 50 as a surface protection film, even if a heat treatment at a high temperature such as a crystallization treatment of the ITO film is performed, the adhesive resin layer is not formed on the ITO film. It is difficult for the adhesive residue phenomenon that a part remains to occur. Therefore, it is possible to perform heat treatment such as crystallization treatment of the ITO film while suppressing contamination of the ITO film.

The base material layer 90 is preferably a soft material that is colorless and transparent in the visible light region and can form an ITO film. Examples thereof include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); cycloolefin resins; polycarbonate resins; polyimide resins; cellulose resins. Among these, polyethylene terephthalate and cycloolefin resins are preferable.

The method of forming the ITO film on the base material layer 90 is not particularly limited as long as it can form a uniform thin film. For example, sputtering, vapor deposition, various CVD, spin coating method, roll coating method, spray coating, dipping coating and the like can be mentioned.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted.

It should be noted that the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

<Material>
Details of the materials used for producing the adhesive laminated film are as follows.

Substrate layer 1: polypropylene (PP) film (manufactured by Toray Film Co., product name: 3701J, thickness: 40 μm)
Cross-linking agent 1: sorbitol polyglycidyl ether (manufactured by Nagase Chemtex, product name: Denacol EX-614)
Surfactant 1: Polyoxyethylene alkyl ether (manufactured by Kao, product name: Emulgen 705)
Organic solvent 1: Diethylene glycol monobutyl ether

(Adhesive resin 1)
51.69 parts by mass of deionized water, 0.23 parts by mass of potassium persulfate as a polymerization initiator, 19.30 parts by mass of 2-ethylhexyl acrylate, and butyl acrylate 19.30 in a polymerization reactor equipped with a reflux condenser. Parts by mass, 3.68 parts by mass of acrylonitrile, 2.30 parts by mass of methacrylic acid, 2.76 parts by mass of acrylamide, 0.23 parts by mass of divinylbenzene, and 0.51 parts by mass of sodium alkyldiphenyl ether disulphonate as a surfactant. Then, emulsion polymerization was carried out at 70° C. for 8 hours with stirring under a nitrogen atmosphere, and the obtained emulsion was neutralized with 25% aqueous ammonia. Through the above procedure, an adhesive resin solution containing 44.5% by mass of adhesive resin 1 was obtained.

(Adhesive resin 2)
In a polymerization reactor equipped with a reflux condenser, 54.81 parts by mass of deionized water, 0.22 parts by mass of potassium persulfate as a polymerization initiator, 25.40 parts by mass of butyl acrylate, 12.41 parts by mass of methyl methacrylate, 2-Hydroxyethyl methacrylate 4.00 parts by mass, methacrylic acid 0.89 parts by mass, acrylamide 0.45 parts by mass, glycidyl methacrylate 1.33 parts by mass, sodium alkyldiphenyl ether disulphonate 0.49 as a surfactant. By mass addition, emulsion polymerization was carried out at 70° C. for 8 hours with stirring under a nitrogen atmosphere, and the obtained emulsion was neutralized with 25% aqueous ammonia. Through the above procedure, an adhesive resin solution containing 45.0% by mass of the adhesive resin 2 was obtained.

(Adhesive resin 3)
In a polymerization reactor equipped with a reflux condenser, 54.78 parts by mass of deionized water, 0.22 parts by mass of potassium persulfate as a polymerization initiator, 29.39 parts by mass of butyl acrylate, 10.23 parts by mass of acrylonitrile and methacrylic acid. 2-Hydroxyethyl 1.77 parts by mass, acrylic acid 1.78 parts by mass, acrylamide 1.34 parts by mass, and sodium alkyldiphenyl ether disulphonate 0.49 parts by mass as a surfactant are added and stirred under a nitrogen atmosphere. On the other hand, emulsion polymerization was carried out at 70° C. for 8 hours, and the obtained emulsion was neutralized with 25% ammonia water. By the above procedure, an adhesive resin solution containing 44.5 mass% of the adhesive resin 3 was obtained.

[Example 1]
The components were mixed in the proportions shown in Table 1 to obtain adhesive 1. The pH was adjusted to 7 using ammonia water, and the viscosity was adjusted to 100 mPa·s using pure water as the adhesive.
The pressure-sensitive adhesive 1 was applied onto the base material layer 1 and then dried to form a pressure-sensitive adhesive resin layer having a thickness of 5 μm to obtain a pressure-sensitive adhesive laminated film.
The following evaluation was performed about the obtained adhesive laminated film. The results obtained are shown in Table 1.

[Examples 2 to 11 and Comparative Example 1]
Adhesive laminated films were obtained in the same manner as in Example 1 except that the adhesives prepared in the proportions shown in Table 1 were used instead of the adhesives 1. The pH was adjusted to a range of 6.5 to 8.5 using aqueous ammonia, and the viscosity of each adhesive was adjusted to 100 to 200 mPa·s using pure water.
The following evaluation was performed about the obtained adhesive laminated film. The results obtained are shown in Table 1.

<Evaluation>
(1) peel strength _{P 0} between the measurement ITO film and the adhesive resin layer of the peel strength _{P 0} conforms to JIS Z0237, was measured by the following method.
Stick the sticky laminated film on the ITO film under the conditions of pressure 2 kg/cm and sticking speed 2 m/min so that the sticky resin layer contacts the ITO film (P02, manufactured by Zhuo Electronics) on the polyester film. It was Then, using a tensile tester (RTA-1210A manufactured by ORITEC), the adhesive laminated film was peeled from the ITO film in the 180° direction at 23° C. and a pulling speed of 300 mm/min, and the strength at that time ( N/25 mm) was defined as the peel strength (P ₀ ).

(2) peel strength _{P 1} between the measurement ITO film and the adhesive resin layer of the peel strength _{P 1} conforms to JIS Z0237, was measured by the following method.
The adhesive laminate film was attached to the ITO film so that the adhesive resin layer was in contact with the ITO film (P02, manufactured by Zhuo Electronics) on the polyester film. Then, the obtained structure was heat-treated at 150° C. for 60 minutes.
Then, using a tensile tester (RTA-1210A manufactured by ORITEC), the adhesive laminated film was peeled from the ITO film in the 180° direction at 23° C. and a pulling speed of 300 mm/min, and the strength at that time ( N/25 mm) was defined as the peel strength (P ₁ ).

(3) Adhesive residue After measuring the peel strength P ₁ , the adhesive residue of the adhesive laminated film on the release surface on the ITO film side was visually observed, and the adhesive residue of the adhesive laminated film was evaluated according to the following criteria.
⊚: Adhesive residue was not observed on the peeling surface on the ITO film side by visual observation, and was good. ◯: Adhesive residue was slightly observed on the peeling surface on the ITO film side, but was generally good. X: Adhesive residue was visually observed on the entire peeling surface on the ITO film side, which was defective.

The adhesive laminated film of the example having an adhesive resin layer containing a structural unit derived from (meth)acrylonitrile has suppressed adhesive residue on the ITO film when heat treatment is performed in a state of being attached to the ITO film. It was
On the other hand, the adhesive laminated film of the comparative example including the adhesive resin layer that does not contain the structural unit derived from (meth)acrylonitrile, has the peeling on the ITO film side when the heat treatment is performed in the state of being attached to the ITO film. Adhesive residue was observed on the entire surface.

10 Base Material Layer 20 Adhesive Resin Layer 50 Adhesive Laminated Film 70 ITO Film 90 Base Material Layer 100 Structure

Claims (8)

An adhesive laminated film for protecting the surface of an indium tin oxide (ITO) film, comprising:
A base material layer and an adhesive resin layer provided on one surface of the base material layer,
An adhesive laminated film in which the adhesive resin layer contains a structural unit derived from (meth)acrylonitrile. In the adhesive laminated film according to claim 1,
The content of the structural unit derived from the (meth)acrylonitrile in the adhesive resin layer is 10% by mass or more and 30% by mass or less when the entire amount of the adhesive resin layer is 100% by mass. .. The adhesive laminated film according to claim 1,
The adhesive resin layer contains a (meth)acrylic adhesive resin, and the (meth)acrylic adhesive resin contains a structural unit derived from the (meth)acrylonitrile. The pressure-sensitive adhesive laminated film according to any one of claims 1 to 3,
Peel strength (P ₀ ) between the ITO film deposited on the substrate film and the adhesive resin layer, measured by the following method, is 0.01 N/25 mm or more and 1.0 N/25 mm or less. Laminated film.
(Peeling strength measurement method)
The adhesive laminated film is attached to the ITO film so that the adhesive resin layer contacts the ITO film deposited on the base film. Then, using a tensile tester, the pressure-sensitive adhesive laminated film was peeled from the ITO film in the 180° direction under the conditions of 23° C. and a pulling speed of 300 mm/min, and the strength (N/25 mm) at that time was peeled. And The pressure-sensitive adhesive laminated film according to any one of claims 1 to 4,
When the adhesive laminate film is attached to the ITO film so that the adhesive resin layer is in contact with the ITO film deposited on the substrate film, and then the obtained structure is heat-treated at 150° C. for 60 minutes ,
The peel strength (P ₁ ) between the ITO film deposited on the substrate film and the adhesive resin layer, measured by the following method, is 0.1 N/25 mm or more and 1.0 N/25 mm or less. Adhesive laminated film.
(Peeling strength measurement method)
Using a tensile tester, the adhesive laminated film was peeled from the ITO film in the direction of 180 degrees under the conditions of 23° C. and a pulling speed of 300 mm/min, and the strength (N/25 mm) at that time was taken as the peel strength. .. The pressure-sensitive adhesive laminated film according to any one of claims 1 to 5,
An adhesive laminate film in which the adhesive resin layer has a thickness of 1 μm or more and 50 μm or less. The pressure-sensitive adhesive laminated film according to any one of claims 1 to 6,
The resin constituting the base material layer is polyolefin, polyester, polyamide, polyacrylate, polymethacrylate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyetherimide, ethylene/vinyl acetate copolymer, polyacrylonitrile, polycarbonate, polystyrene. A pressure-sensitive adhesive laminated film containing one or more selected from ionomers, polysulfones, polyether sulfones and polyphenylene ethers. An indium tin oxide (ITO) film,
A surface protection film attached to the ITO film,
A structure, wherein the surface protective film is the adhesive laminated film according to any one of claims 1 to 7.

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